Branched olefinic macromonomer, olefin graft copolymer, and olefin resin composition

ABSTRACT

The invention relates to olefin branched macromonomers, olefin graft copolymers and olefin resin compositions having the advantage of good compatibility with polyolefin resins and good moldability and workability. The olefin branched macromonomer satisfies the following (a) and (b):
         (a) its weight-average molecular weight (Mw) measured through gel permeation chromatography (GPC) falls between 400 and 200000;   (b) its vinyl content is at least 70 mol % of all the unsaturated groups in the macromonomer.

TECHNICAL FIELD

The present invention relates to olefin branched macromonomers, olefingraft copolymers and olefin resin compositions having the advantages ofgood compatibility with polyolefin resins and good moldability andworkability.

BACKGROUND ART

Polyolefins are thermoplastic resins having good chemical stability,good moldability and workability, and good mechanical properties, and,in addition, they are easy to recycle. Another advantage of the resinsis that they give few harmful substances when incinerated. Therefore, itis believed that their applications will further increase in future. Fortheir prospects in the field of polyolefin industry, it is expected thatthe resins having such good characteristics intrinsic thereto arefurther improved to make them have better properties to thereby expandtheir applications further more. For this, it is considered that oneeffective means is to compound different types of polyolefins into resincomposites. For compounding them, it is an important technique to usecompatibilizer. In the technical field that requires more high-levelworkability of resins, for example, in the field of large-size blowmolding, expansion foaming through extrusion, sheet forming andthermoforming, it is desired to further improve the moldability and theworkability of resins. For improving the moldability and the workabilityof resins, for example, branched polyolefins may be used for improvingthe melt flowability of resins.

In the related art technique, it is said that propylene macromonomersare employable as compatibilizers for polyolefin resins. Regardingpropylene macromonomers, disclosed are a method for producing propyleneprepolymers (Japanese Patent Laid-Open Nos. 207248/1989, 25215/1993);and a method of modifying vinylidene-type unsaturated terminals tothereby introduce a polar group thereinto (Japanese Patent Laid-Open No.259582/1996). The former produces dimers such as 4-methylpentene-1, andits problem is that the degree of polymerization of the products is low.In the latter, the products produced are not copolymerizable as they arevinylidene-terminated, and a vinyl group must be introduced thereinto.Anyhow, the products of these methods are unsuitable forcompatibilizers.

On the other hand, for one example of compounding different types ofpolyolefins, mentioned are graft copolymers. Some examples of graftpolymers are disclosed in Japanese Patent Laid-Open No. 230717/1988 andInternational Patent Publication No. 502308/1996, but their meltworkability and compatibility are not still so good.

The present invention is to provide novel olefin branched macromonomers,olefin graft copolymers, as well as propylene macromonomers, propylenegraft copolymers, and also olefin resin compositions having goodcompatibility with polyolefin resins and having good moldability andworkability.

DISCLOSURE OF THE INVENTION

We, the present inventors have assiduously studied in consideration ofthe above-mentioned viewpoints, and, as a result, have found that olefinbranched macromonomers, olefin graft copolymers, as well as propylenemacromonomers, propylene graft copolymers, and olefin resin compositionshaving specific primary structures and specific solution properties canattain the object of the invention. On the basis of these findings, wehave completed the invention.

The invention provides olefin branched macromonomers, olefin graftcopolymers and olefin resin compositions mentioned below (hereinafterreferred to as “the first aspect of the invention”), and providespropylene macromonomers, propylene graft copolymers and olefin resincompositions mentioned below (hereinafter referred to as “the secondaspect of the invention”).

Specifically, the first aspect of the invention is as follows:

1. An olefin branched macromonomer satisfying the following (a) and (b):

(a) its weight-average molecular weight (Mw) measured through gelpermeation chromatography (GPC) falls between 400 and 200000;

(b) its vinyl content is at least 70 mol % of all the unsaturated groupsin the macromonomer.

2. The olefin branched macromonomer of above 1, which satisfies any ofthe following (i), (ii) and (iii):

(i) the ratio of the temperature dependency (E₂) of the macromonomersolution viscosity to the temperature dependency (E₁) of the solutionviscosity of the linear polymer which has the same type of monomer, thesame chemical composition and the same intrinsic viscosity as those ofthe macromonomer, E₂/E₁, satisfies the following relationship:1.01≦E ₂ /E ₁≦2.5;

(ii) the ratio of the number-average molecular weight measured throughGPC (GPC-Mn) to the number-average molecular weight measured through¹³C-NMR (NMR-Mn) of the macromonomer satisfies the followingrelationship:(GPC-Mn)/(NMR-Mn)>1;

(iii) the macromonomer has branches existing not at the α- and/orβ-substituents of the monomer that constitutes the macromonomer, and thenumber of the branches falls between 0.01 and 40 in one molecule of themacromonomer.

3. The olefin branched macromonomer of above 1 or 2, for which themonomer to constitute it is propylene, or a combination of propylene andat least one selected from ethylene, α-olefins having from 4 to 20carbon atoms, cyclic olefins and styrenes, and of which the propylenecontent falls between 0.1 and 100 mol %.

4. The olefin branched macromonomer of above 1 or 2, for which themonomer to constitute it is ethylene, or a combination of ethylene andat least one selected from α-olefins having from 4 to 20 carbon atoms,cyclic olefins and styrenes, and of which the ethylene content fallsbetween 50 and 99.9 mol %.

5. The olefin branched macromonomer of above 1 or 2, for which themonomer to constitute it is ethylene or propylene.

6. An olefin graft copolymer obtained by copolymerizing the olefinbranched macromonomer of any of above 1 to 5 with at least one comonomerselected from ethylene, propylene, α-olefins having from 4 to 20 carbonatoms, cyclic olefins and styrenes, in the presence of a metallocenecatalyst.

7. An olefin graft copolymer obtained by copolymerizing the olefinbranched macromonomer of any of above 1 to 5 with at least one comonomerselected from ethylene, propylene, α-olefins having from 4 to 20 carbonatoms, cyclic olefins and styrenes, in the presence of a Ziegler-Nattacatalyst.

8. The olefin graft copolymer of above 6 or 7, which satisfies thefollowing (1) and/or (2):

(1) its intrinsic viscosity [η] measured in a solvent decalin at 135° C.falls between 0.3 and 15 dl/g;

(2) it contains from 0.01 to 70% by weight of the olefin branchedmacromonomer of any of above 1 to 5.

9. An olefin resin composition comprising 100 parts by weight of athermoplastic resin, and from 0.05 to 70 parts by weight of the olefingraft copolymer of any of above 6 to 8.

10. The olefin resin composition of above 9, of which the relaxationrate of the long-term relaxation component measured through solid ¹H-NMR(1/R₁) falls between 1.0 and 2.0 (1/sec).

11. The olefin resin composition of above 9 or 10, of which the ratio ofthe relaxation rate (1/R₁) of above 10 to the relaxation rate (1/R₁)₀ ofthe long-term relaxation component, measured through solid ¹H-NMR, of aresin composition not containing the propylene branched macromonomer ofany of above 1 to 5, [(1/R₁)/(1/R₁)₀], satisfies the followingrelationship:[(1/R ₁)/(1/R ₁)₀]≧1.01.

The second aspect of the invention is as follows:

1. A propylene macromonomer satisfying the following (a), (b) and (c):

(a) its weight-average molecular weight (Mw) measured through gelpermeation chromatography (GPC) falls between 800 and 500000;

(b) its vinyl content is at least 70 mol % of all the unsaturated groupsin the macromonomer;

(c) its propylene content falls between 50 and 100 mol %.

2. The propylene macromonomer of above 1, for which the monomer toconstitute it is propylene, or a combination of propylene and at leastone selected from ethylene, α-olefins having from 4 to 20 carbon atoms,cyclic olefins and styrenes.

3. The propylene macromonomer of above 1 or 2, for which the monomer toconstitute it is ethylene and propylene.

4. An olefin graft copolymer obtained by copolymerizing the propylenemacromonomer of any of above 1 to 3 with at least one comonomer selectedfrom ethylene, propylene, α-olefins having from 4 to 20 carbon atoms,cyclic olefins and styrenes, in the presence of a metallocene catalyst.

5. An olefin graft copolymer obtained by copolymerizing the propylenemacromonomer of any of above 1 to 3 with at least one comonomer selectedfrom ethylene, propylene, α-olefins having from 4 to 20 carbon atoms,cyclic olefins and styrenes, in the presence of a Ziegler-Nattacatalyst.

6. The olefin graft copolymer of above 4 or 5, which contains from 0.01to 40% by weight of the propylene macromonomer of any of above 1 to 3.

7. The propylene graft copolymer of any of above 4 to 6, which satisfiesthe following (1) and/or (2):

(1) its intrinsic viscosity [η] measured in a solvent decalin at 135° C.falls between 0.3 and 15 dl/g;

(2) the ratio of the weight-average molecular weight (Mw) to thenumber-average molecular weight (Mn) thereof measured through GPC,Mw/Mn, falls between 1.5 and 4.5.

8. An olefin resin composition comprising 100 parts by weight of athermoplastic resin, and from 0.05 to 70 parts by weight of thepropylene graft copolymer of any of above 4 to 7.

9. The olefin resin composition of above 8, of which the relaxation rateof the long-term relaxation component measured through solid ¹H-NMR(1/R₁) falls between 1.0 and 2.0 (1/sec).

10. The olefin resin composition of above 8 or 9, of which the ratio ofthe relaxation rate (1/R₁) of above 9 to the relaxation rate (1/R₁)₀ ofthe long-term relaxation component, measured through solid ¹H-NMR, of aresin composition not containing the propylene graft copolymer of any ofabove 4 to 7, [(1/R₁)/(1/R₁)₀], satisfies the following relationship:[(1/R ₁)/(1/R ₁)₀]≧1.01.

BEST MODES OF CARRYING OUT THE INVENTION

Embodiments of the invention are described below.

I. First Aspect of the Invention:

In this section, the first aspect of the invention will be simplyreferred to as “the invention”.

As in the above, the invention provides olefin branched macromonomers,olefin graft copolymers and olefin resin composition.

The olefin branched macromonomer [1], the olefin graft copolymer [2] andthe olefin resin composition [3] of the invention are described indetail hereinunder.

[1] Olefin Branched Macromonomer:

The olefin branched macromonomer of the invention satisfies thefollowing (a) and (b):

(a) its weight-average molecular weight (Mw) measured through gelpermeation chromatography (GPC) falls between 400 and 200000;

(b) its vinyl content is at least 70 mol % of all the unsaturated groupsin the macromonomer.

The olefin branched macromonomer of the invention (hereinafter this willbe referred to as “the macromonomer”) has a low to middle-levelmolecular weight, and has side chains, in which the main chain or someside chains are vinyl-terminated. Since the macromonomer has side chainsand contains many vinyl groups, it is effective in various chemicalreactions such as typically grafting reaction. In addition, since itsmolecular weight falls in a broad range of from relatively low to highmolecular weights, it is usable as the material for compatibilizers forvarious resins and also as a resin moldability improver.

The weight-average molecular weight (Mw) of the macromonomer of theinvention, measured through GPC, falls between 400 and 200000, butpreferably between 500 and 180000, more preferably between 600 and150000, even more preferably between 700 and 130000, most preferablybetween 900 and 100000. Macromonomers having Mw of smaller than 400 areuseless in production of graft copolymers, as their ability to improveresin compatibility and resin melt tension is not good; but those havingMw of larger than 200000 are unfavorable since the apparent terminalvinyl content thereof is extremely small and the graft copolymerizationefficiency with them is poor.

For GPC for the invention, the following method is employable.

Method of GPC:

-   -   Device: Waters 150C        -   detector, RI        -   column, TOSO GMHHR-H(S)HT    -   Solvent: 1,2,4-trichlorobenzene    -   Temperature: 145° C.    -   Flow Rate: 1.0 ml/min    -   Calibration Curve: Universal Calibration    -   Sample Concentration: 0.2%

In the invention, the vinyl content of the macromonomer falls between 70and 100% of all the unsaturated groups in the macromonomer. Preferably,it falls between 75 and 100%, more preferably between 80 and 100%, mostpreferably between 85 and 100%. If the vinyl content is smaller than70%, the efficiency in grafting reaction with the macromonomer is low,and the residual macromonomer lowers the physical properties of graftpolymers.

The vinyl content relative to all the unsaturated groups in themacromonomer may be measured according to the following method (1)through ¹H-NMR, or (2) through IR.

(1) ¹H-NMR Method:

From the data of ¹H-NMR, the peaks are assigned as follows:

-   -   4.8 ppm to 5.1 ppm: methylene proton of vinyl group    -   5.6 ppm to 5.85 ppm: methine proton of vinyl group    -   4 ppm to 6 ppm except the above peaks: other unsaturated bonds        such as vinylidene group

The vinyl content relative to all the unsaturated groups in themacromonomer is calculated in terms of the percentage of the vinylgroups to all the unsaturated groups in the macromonomer appearingwithin the range of from 4 ppm to 6 ppm.

(2) IR Method:

The sample to be measured is formed into a press sheet, and this issubjected to IR absorption spectrometry. From the IR data, the vinylcontent is determined as follows: The macromonomer has the followingthree types of carbon—carbon unsaturated double bonds. Their peakpositions are as in the following Table, and their data are obtainedaccording to the formulae therein.

Unsaturated Bond Peak Position Calculation trans 963 cm⁻¹ Nt =0.083A₉₆₃/(ρ·t) terminal vinyl 907 cm⁻¹ Nv = 0.114A₉₀₇/(ρ·t) vinylidene888 cm⁻¹ Nvd = 0.109A₈₈₈/(ρ·t) Nt, Nv, Nvd: the number of theunsaturated bonds per 100 carbons. A: absorbance. ρ: resin density(g/cc). T: sample thickness (mm).

The terminal vinyl selectivity in the macromonomer is represented by:Nv/(Nt+Nv+Nvd)×100 (%).

The macromonomer of the invention has branches, and the “branches”therein are not specifically defined so far as they are caused by thedifference in the structure between branched macromonomers andnon-branched, or that is, linear macromonomers. The structuraldifference between them includes, for example, the differencestherebetween in the temperature dependence of solution viscosity, theterminal group structure, the stereospecificity, and the compositionalratio. More concretely, the “branches” may be specified by the following(i), (ii) and (iii). Any of these may apply to the present invention.

(i) Branches detected from the temperature dependence of solutionviscosity:

For its branches, the macromonomer of the invention preferably satisfiesthe following requirement:1.01/E ₂ /E ₁≦2.5.This indicates the ratio, E₂/E₁, of the temperature dependency (E₂) ofthe macromonomer solution viscosity to the temperature dependency (E₁)of the solution viscosity of the linear polymer which has the same typeof monomer, the same chemical composition and the same intrinsicviscosity as those of the macromonomer, in which E₂ and E₁ are obtainedaccording to the method of measuring the temperature dependency ofpolymer solution viscosity mentioned below.More preferably, it satisfies1.03≦E ₂ /E ₁/2.5,even more preferably,1.04≦E ₂ /E ₁≦2.5,most preferably,1.05≦E ₂ /E ₁≦2.5.

If the ratio is smaller than 1.01, the branch formation in themacromonomer is unsatisfactory, and the polymers obtained throughgrafting with the macromonomer are ineffective for improving the meltworkability and the compatibility of polyolefin resins. On the otherhand, in the macromonomer of which the ratio is larger than 2.5, thebranch formation is good, but the macromonomer of the type lowers themechanical properties of the graft polymers with it, and is thereforeunfavorable.

The method for measuring the temperature dependency (E₂, E₁) of polymersolution viscosity is described in detail. In the invention, thetemperature dependency (E₂, E₁) is measured according to the method thatcomprises the steps <1> to <4> mentioned below.

<1> Preparation of Linear Polymer:

To measure its E₁, a sample of the linear polymer is prepared. In casewhere the macromonomer of the invention is a homopolymer, prepared is alinear homopolymer having the same type of monomer and having the sameintrinsic viscosity [η] measured in a solvent decalin at 135° C. asthose of the homo-macromonomer. For example, the linear homopolymer maybe prepared by polymerizing a monomer in a toluene solvent in thepresence of a polymerization catalyst of Cp₂ZrCl₂/methylaluminoxane(Al/Zr≧500 by mol). The intrinsic viscosity of the linear homopolymermay be controlled in any ordinary manner, for example, by controllingthe polymerization pressure, the monomer concentration, thepolymerization temperature, the catalyst amount and the degree ofhydrogen introduction. The difference between the intrinsic viscosity ofthe linear homopolymer thus prepared and that of the branchedhomopolymer (macromonomer) of the invention prepared according to methodmentioned below must be within the range of ±10%.

In case where the macromonomer of the invention is a copolymer, preparedis a linear copolymer having the same type of monomer, the samecopolymerization composition and the same intrinsic viscosity [η]measured in a solvent decalin at 135° C. as those of theco-macromonomer. For example, the linear copolymer may be prepared bycopolymerizing at least two different types of monomers in a toluenesolvent in the presence of a polymerization catalyst ofCp₂ZrCl₂/methylaluminoxane (Al/Zr≧500 by mol). The intrinsic viscosityof the linear copolymer may be controlled in any ordinary manner, forexample, by controlling the olefin concentration, the polymerizationpressure, the polymerization temperature, the catalyst amount and thedegree of hydrogen introduction. The copolymerization referred to hereinindicates the polymerization system in which at least two differenttypes of monomers are previously mixed and then copolymerized in theform of their mixture. The difference between the intrinsic viscosity ofthe linear copolymer thus prepared and that of the branched copolymer(macromonomer) of the invention prepared according to method mentionedbelow, and the difference therebetween in the copolymerizationcomposition must be both within the range of ±10%. The linearhomopolymer and copolymer may be or may not be vinyl-terminated.

Except that mentioned hereinabove, the polymerization catalyst usable inobtaining the linear homopolymer and copolymer includes Ziegler-Nattacatalysts comprising a transition metal compound of Group 4 of thePeriodic Table and an organoaluminium compound (e.g., in Japanese PatentPublication No. 3356/1978), and high-activity Ziegler-Natta catalystscomprising a catalyst component prepared through contact of a magnesiumcompound with a titanium compound in the presence or absence of anelectron donor, and an organoaluminium compound (e.g., in JapanesePatent Laid-Open Nos. 43094/1978, 135102/1980, 135103/1980, 18606/1981).

The transition metal compound of Group 4 of the Periodic Table for theZiegler-Natta catalysts includes transition metal halides. For thetransition metal halides, preferred are titanium halides, and morepreferred is titanium trichloride. Titanium trichloride may be obtainedin various methods. For example, titanium tetrachloride is reduced inany desired manner; the product obtained through the reduction isactivated by milling it in a ball mill and/or by washing it with asolvent (for example, in an inert solvent and/or a polarcompound-containing inert solvent); titanium trichloride or titaniumtrichloride eutectoids (e.g., TiCl₃+(⅓)AlCl₃) are further co-groundalong with any of amines, ethers, esters, sulfur derivatives, halogenderivatives, organic or inorganic nitrogen compounds or phosphoruscompounds; or titanium trichloride having been liquefied in the presenceof an ether compound is crystallized. In addition, those obtainedaccording to the method described in Japanese Patent Publication No.3356/1978 are also employable.

The magnesium compound includes, for example, metal magnesium, magnesiumhalides (e.g., magnesium chloride), and magnesium alkoxides (e.g.,magnesium diethoxide).

The electron donor includes, for example, alcohols (e.g., ethanol) andesters (e.g., benzoates). For the organoaluminium compound serving asthe other component of the catalysts, preferred are compounds of aformula, AlR_(n)X_(3-n), in which R represents an alkyl group havingfrom 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbonatoms, or an aryl group having from 6 to 10 carbon atoms; X represents ahalogen atom; and n is a value satisfying 0<n≦3. Concretely, theyinclude triethylaluminium, triisobutylaluminium, tri-n-propylaluminium,diethylaluminium monochloride, diethylaluminium monobromide,diethylaluminium monoiodide, diethylaluminium monoethoxide,diisobutylaluminium monoisobutoxide, diethylaluminium monohydride,diisobutylaluminium monohydride, ethylaluminium sesquichloride,ethylaluminium dichloride. One or more of these may be used for thecatalyst.

<2> Determination of Sample Concentration:

The solution viscosity of the linear polymer, homopolymer or copolymerprepared according to the method mentioned above, and that of themacromonomer of the invention to be prepared according to the methodmentioned below are measured, for which the concentration of the samplemay be controlled in the following manner. Concretely, the concentrationof the olefin branched macromonomer of the invention and that of thecontrol, linear polymer prepared as in the above <1> are so controlledthat the relative viscosity of the two may be on the same level within arange of from 3 to 10, at a temperature predetermined for themeasurement. For this, the relative viscosity of the two must be thesame, not overstepping a difference of ±5% therebetween. Their relativeviscosity is measured in a solvent of trichlorobenzene (TCB) at atemperature predetermined within a range of from 40° C. to 145° C.

<3> Measurement of Temperature Dependency of Relative Viscosity:

The relative viscosity of the TCB solution of each sample, of which thesample concentration has been determined in the above <2>, is measuredat different temperatures. The condition for the measurement may be asfollows:

-   -   Temperature Range for Measurement: 40° C. to 145° C.    -   Points for Measurement: Each sample is measured at least at 4        points, for which the temperature difference between the        adjacent points is at least 10° C.    -   Accuracy of Temperature for Measurement: set point ±0.05° C.    -   Frequency of Measurement: One sample is measured at least 5        times at the same temperature. The highest value and the lowest        value are omitted, and the remaining data are averaged.    -   Viscometer: Ubbellohde viscometer.    -   Solvent: TCB (containing 1000 ppm of antioxidant, BHT).        <4> Evaluation:

The data are plotted in coordinates, of which the X-axis indicates thereciprocal of the temperature (absolute temperature) for measurement,and the Y-axis indicates the logarithmic number of the relativeviscosity (T₁/T₀; T₁ is the viscosity of the solution, and T₀ is theviscosity of the solvent alone), or indicates the logarithmic number ofT₁ itself. A straight line is drawn through linear regression of theplotted curve. From the inclination of the straight line, E₁ of thelinear polymer and E₂ of the olefin branched macromonomer of theinvention are determined through least square approximation. In casewhere T₁ itself is for the Y-axis herein, it is natural that the sameviscometer showing the same blank value (T₀) should used for the two,the control linear polymer and the macromonomer of the invention.

(ii) Branches detected from the ratio of the number-average molecularweight measured through GPC to that measured through ¹³C-NMR:

The ratio of the number-average molecular weight measured through GPC(GPC-Mn) to the number-average molecular weight measured through ¹³C-NMR(NMR-Mn) of the macromonomer of the invention satisfies the followingrelationship:(GPC-Mn)/(NMR-Mn)>1.

Specifically, the ratio, (GPC-Mn)/(NMR-Mn), of the number-averagemolecular weight measured through GPC (GPC-Mn) of the macromonomer ofthe invention, to the number-average molecular weight thereof measuredthrough ¹³C-NMR (NMR-Mn) (for this, the terminal groups in themacromonomer are quantified through ¹³C-NMR, and the number-averagemolecular weight of the macromonomer is derived from the data of theterminal groups) is larger than 1. Preferably, the ratio falls between 1and 10, more preferably between 0.05 and 8, most preferably between 1.1and 7. If the ratio is 1 or less, the number of the branches in themacromonomer is small or the macromonomer has no branches. If themacromonomer of the type is used in producing graft polymers, theresulting graft polymers are unfavorable since they are ineffective forimproving the melt workability and the compatibility of polyolefinresins.

How to obtain these (GPC-Mn) and (NMR-Mn) is described in detailhereinunder.

<How to obtain (GPC-Mn)>

Using the device mentioned above and according to the method alsomentioned above, the molecular weight of the macromonomer of theinvention is measured. For example, in case where the macromonomer ofthe invention is a PP polymer, its number-average molecular weight (Mn)in terms of propylene is divided by the molecular weight of propylene,and the number of monomer molecules in one molecule of the macromonomer(GPC-Mn) is thus obtained. In case where it is a PE polymer, its numbernumber-average molecular weight (Mn) in terms of ethylene is divided bythe molecular weight of ethylene, and the number of monomer molecules inone molecule of the macromonomer (GPC-Mn) is thus obtained.

<How to obtain (NMR-Mn)>

The terminals of the macromonomer of the invention comprise anunsaturated terminal group such as vinyl, vinylidene or vinylene group,and a saturated terminal alkyl group such as, for example, n-butyl,isobutyl or propyl group. The macromonomer is subjected to ¹³C-NMR forthese terminal groups, through which the presence and the quantity ofthe individual terminal groups are determined. Based on the results, theratio of the number of monomer molecules to that of terminalsconstituting the main chain of the macromonomer is obtained, and thisindicates the number of monomer molecules in one molecule of themacromonomer (NMR-Mn). Concretely, in case where the macromonomer of theinvention is a homopolymer, the relative intensity (Im) corresponding tothe number of monomer molecules constituting the macromonomer isdetermined from the absorption peaks for any of methyl, methylene ormethine group appearing in the NMR pattern.

From the absorption peaks corresponding to the terminal groups mentionedabove, the total sum of the relative intensity (Ie) corresponding to thenumber of the terminal groups is determined. On the presumption that themacromonomer is not branched and that the number of the terminals of thenon-branched macromonomer is two, the number of the monomer molecules inone macromonomer molecule, (NMR-Mn) is represented as follows:NMR-Mn=2(Im)/(Ie).

In case where the macromonomer of the invention is a copolymer, therelative intensity (Im) thereof that corresponds to the number ofmonomer molecules constituting the main chain of the copolymer isdetermined from the absorption peaks peculiar to the monomersconstituting the main chain and from the copolymerization composition ofthe copolymer, and the other factors are determined in the same manneras that for the homopolymer. From these, the number of monomer moleculesin one macromonomer molecule, NMR-Mn is determined.

(NMR-Mn) and (GPC-Mn) obtained in the manner as above are compared witheach other.

(NMR-Mn) is calculated and determined on the presumption that themacromonomer has no branch. For branched macromonomers, therefore, thisis estimated to be smaller than the actual molecular weight, and thereis a difference between it and (GPC-Mn). In order that the presence ofbranches in the macromonomer is clarified according to this method, itis desirable that a sample of an obviously linear polymer is measured tocalculate its molecular weight according to the method as above, and theratio to the thus-calculated molecular weight of the sample is used as afactor. More preferably, samples of obviously linear polymers thatdiffer in the molecular weight are measured to determine the factor.Using the thus-determined factor, the accuracy in clarifying thepresence of the branches in the macromonomer is increased. The obviouslylinear samples referred to herein are those of the polymer producedaccording to the method mentioned hereinunder. With the factor, f, thepresence of the branches in the macromonomer is represented moreaccurately by f×[(GPC-Mn)/(NMR-Mn)], and this is more preferred in theinvention. (iii) The macromonomer has branches existing not at the α-and/or β-substituents of the monomer molecules that constitute themacromonomer, and the number of the branches falls between 0.01 and 40in one molecule of the macromonomer. The method for measuring (iii) isdescribed concretely. It includes the following three methods <1>, <2>and <3>. In the invention, any of these methods is employable. Thesummary of these methods is described.

<1> Method of GPC:

The amount of the oligomer molecules fed into the reaction system forforming the side chains of the macromonomer, and the amount of thenon-reacted oligomer molecules that have remained in the system afterthe branch-forming reaction are quantified, and the amount of thebranches in the macromonomer formed is determined from thethus-quantified data.

<2> Method of Composition Analysis:

This is for branched macromonomers which comprise side chains and a mainchain having a sequence completed after the branch-forming reaction andin which some types of monomer molecules are only in the side chains butnot in the main chain. The branched macromonomers of the type areanalyzed for the copolymerization composition, and the branches thereinare quantified.

<3> Method of Stereospecificity Analysis:

This is for branched macromonomers in which the side chainssignificantly differ from the main chain having a sequence completedafter the branch-forming reaction in point of the stereospeciticity. Thebranched macromonomers of the type are analyzed for thestereospecificity, and the branches therein are quantified.

These methods are described in detail hereinunder.

<1> Method of GPC:

The reaction mixture after the process of producing a branchedmacromonomer (this is in the form of a mixture of the branchedmacromonomer formed and the side-chain-forming but non-reacted oligomer)is subjected to GPC, through which the ratio (a) of the branchedmacromonomer to the side-chain-forming but non-reacted oligomer isdetermined. Specifically, the ratio, a (%), indicates the proportion ofthe non-reacted oligomer moiety to the total peak area in GPC. In thiscase, when the neighboring peaks are near to each other, the GPC patternis processed for waveform separation. The molecular weight of theside-chain-forming oligomer and the molecular weight distributionthereof can be previously determined. Therefore, the waveform separationof the GPC pattern may be effected with accuracy.

Next, the amount of the side-chain-forming oligomer fed into thepolymerization system is referred to as b (gram); and the yield of thereaction mixture after the production of the branched macromonomer isreferred to c (gram). From these a, b and c, the branches in thebranched macromonomer can be qualified.

Specifically, the amount of the non-reacted oligomer is represented by:c×a/100 (gram).Accordingly, the amount of the oligomer taken in the branchedmacromonomer to form the branches is represented by:b−[c×a/100] (gram).

On the other hand, the actual yield of the branched macromonomer isrepresented by:c(1−a/100) (gram).Accordingly, the weight ratio of the oligomer existing in the branchedmacromonomer as its branches is defined by:{b−[c×a/100]}/[c(1−a/100)] (gram/gram).

In general, this value falls between 0.0001 and 0.7,

-   preferably between 0.0005 and 0.6,-   more preferably between 0.0007 and 0.55,-   even more preferably between 0.0008 and 0.50,-   most preferably between 0.001 and 0.50.

If this value is smaller than 0.0001, the branch formation in themacromonomer is insufficient, and the graft polymers with themacromonomer are ineffective for improving the melt workability and thecompatibility of polyolefin resins. On the other hand, if it is largerthan 0.7, the branch formation in the macromonomer is good, but themacromonomer lowers the graft copolymers with it and is thereforeunfavorable.

The number of branches in one branched macromonomer is represented asfollows:

The number-average molecular weight of the side-chain-forming oligomermeasured through GPC is indicated by (Mn)^(M); and the molecular weightof the monomer (this corresponds to the molecular weight of ethylenewhen GPC is in terms of polyethylene, but corresponds to the molecularweight of propylene when GPC is in terms of polypropylene) is indicatedby M. The weight of the oligomer taken in the above-mentioned, branchedmacromonomer as its side chains is indicated by:{b−[c×a/100]} (gram).From these values, the mean degree of polymerization (Pn) of theside-chain-forming oligomer is indicated by:Pn=(Mn)/M;and the number, m, of the monomer molecules constituting theside-chain-forming oligomer is indicated by:m={b−[c×a/100]}/M (mol).Accordingly, the number of molecules of the side-chain-forming oligomer,m/Pn (mol), is defined as follows:{b−[c×a/100]}/(Mn)^(M) (mol).

In the same manner as above, the number of molecules of the branchedmacromonomer (mol) is calculated.

The number-average molecular weight of the branched macromonomermeasured through GPC is indicated by (Mn)^(B). One method fordetermining this value is based on the data of GPC of the reactionmixture after the production of the branched macromonomer (the mixtureis in the form of the branched macromonomer and the side-chain-formingbut non-reacted oligomer) like that mentioned hereinabove. In case wherethe branched macromonomer is obviously separated from theside-chain-forming but non-reacted oligomer in the reaction mixture, thevalue of (Mn)^(B) is determined from the peaks of the branchedmacromonomer appearing in the high-molecular weight range. In case wherethe neighboring peaks are near to each other, the GPC pattern may beprocessed for waveform separation.

The molecular weight of the side-chain-forming oligomer and themolecular weight distribution thereof can be previously determined.Therefore, the waveform separation of the GPC pattern may be effectedwith accuracy. After the GPC pattern has been thus processed forwaveform separation, (Mn)^(B) is determined from the peaks of thebranched macromonomer appearing in the high-molecular weight range ofthe pattern.

Another method for determining the value (Mn)^(B) is as follows: Theside-chain-forming but non-reacted oligomer is removed from the reactionmixture through solvent fractionation, and (Mn)^(B) is determined fromthe GPC pattern of the thus-fractionated branched macromonomer.

For the solvent to be used in the method, the good solvent includes, forexample, aliphatic hydrocarbon solvents such as hexane, heptane, octane;alicyclic saturated hydrocarbon solvents such as cyclohexane; aromatichydrocarbon solvents such as benzene, toluene, xylene; TCB,decahydronaphthalene; and halogenohydrocarbon solvents such aschlorobenzene, tetrachloroethylene. The bad solvent includes, forexample, alcohols such as isopropanol, hexyl alcohol, ethyl alcohol,methyl alcohol, and ethers. The solvent fractionation may be effected inany ordinary manner, for which the blend ratio of the good solvent andthe bad solvent, the temperature and the temperature pattern may besuitably controlled.

The molecular weight of the monomer (this corresponds to the molecularweight of ethylene when GPC is in terms of polyethylene, but correspondsto the molecular weight of propylene when GPC is in terms ofpolypropylene) is indicated by M; and the actual yield of the branchedmacromonomer mentioned above is indicated by:c(1−a/100) (gram).

Similarly, the number of molecules of the branched macromonomer isindicated by:[c(1−a/100)]/(Mn)^(B) (mol).

Accordingly, the number of the branches existing in one branchedmacromonomer molecule is defined as follows:

The ratio of side-chain-forming oligomer molecules/branched macromonomermolecules is represented by:[{b−(c×a/100)}/{c(1−a/100)}]×[(Mn)^(B)/(Mn)^(M)].In general, this value falls between 0.01 and 40/macromonomer molecule,

-   preferably between 0.05 and 35,-   more preferably between 0.1 and 30,-   even more preferably between 0.15 and 30,-   most preferably between 0.2 and 25.

If this is smaller than 0.01, the branch formation in the macromonomeris unsatisfactory, and the polymers obtained through grafting with themacromonomer are ineffective for improving the melt workability and thecompatibility of polyolefin resins. On the other hand, in themacromonomer of which the ratio is larger than 40, the branch formationis good, but the macromonomer of the type lowers the mechanicalproperties of the graft polymers with it, and is therefore unfavorable.

<2> Method of Composition Analysis:

The number-average molecular weight of the side-chain-forming oligomeris indicated by (Mn)^(M); and the copolymerization composition of themonomer existing only in the side chains is indicated by [(Mc)^(M)] (mol%). The molecular weight of the monomer (this corresponds to themolecular weight of ethylene when GPC is in terms of polyethylene, butcorresponds to the molecular weight of propylene when GPC is in terms ofpolypropylene) is indicated by M. The number of the monomer molecules inone side-chain-forming oligomer molecule is represented by:[(Mn)^(M)/M]·[(Mc)^(M)/100] (mol).

The number-average molecular weight of the branched macromonomer isindicated by (Mn)^(B); and the copolymerization composition of themonomer existing only in the side chains is indicated by [(Mc)^(B)] (mol%). In the same manner as above, the number of the monomer moleculesexisting only in the side chains in one macromonomer is represented by:[(Mn)^(B)/M]·[(Mc)^(B)/100].Accordingly, the number of branches in one branched macromonomermolecule is represented by:[(Mn)^(B)(Mc)^(B)]/[(Mn)^(M)(Mc)^(M)].In general, this value falls between 0.01 and 40/macromonomer molecule,

-   preferably between 0.05 and 35,-   more preferably between 0.1 and 30,-   even more preferably between 0.15 and 30,-   most preferably between 0.2 and 25.

If this is smaller than 0.01, the branch formation in the macromonomeris unsatisfactory, and the polymers obtained through grafting with themacromonomer are ineffective for improving the melt workability and thecompatibility of polyolefin resins. On the other hand, in themacromonomer of which the ratio is larger than 40, the branch formationis good, but the macromonomer of the type lowers the mechanicalproperties of the graft polymers with it, and is therefore unfavorable.

<3> Method of Stereospecificity Analysis:

In this method, the stereospecificity (corresponding to the index of thestereospecificity indicated by the meso-fraction ([mm] % or [mmmm] %) orthe racemi-fraction ([rr] % or [rrrr]%) measured through ¹³C-NMR) of theside-chain-forming oligomers constituting the branched macromonomer isrepresented by (Tc)^(M); and the number-average molecular weight of theoligomers measured through GPC is by (Mn)^(M). The stereospecificity ofthe branched macromonomer is represented by (Tc)^(B); and thenumber-average molecular weight thereof is by (Mn)^(B). Thestereospecificity of the polymer with no side-chain-forming oligomer isrepresented by Tc.

First determined is the ratio of the side chains to the main chain ofthe branched macromonomer, or that is, the sequence ratio of the two inthe branched macromonomer. Based on the additivity of thestereospecificity, (Tc)^(M), of the side-chain-forming oligomer to thestereospecificity, Tc, of the polymer with no side-chain-formingoligomer, the stereospecificity, (Tc)^(B), of the branched macromonomeris represented as follows:(Tc)^(B) =Tc(1−X)+(Tc)^(M) X.

In this, X means the existence ratio of the side-chain-forming oligomerin the branched macromonomer (0<X<1). That is, X is as follows:X=[Tc−(Tc)^(B) ]/[Tc−(Tc)^(M)].

The mean degree of polymerization (Pn) of the side-chain-formingoligomer is:Pn=(Mn)^(M) /M,and the number, m (mol), of the monomer molecules in theside-chain-forming oligomer is:m=X/M (mol).

Accordingly, the number of the side-chain-forming oligomer molecules ism/Pn (mol), and is defined as follows:X/(Mn)^(M) (mol).

Similarly, the number of the branched macromonomer molecules is definedby 1/(Mn)^(B). Accordingly, the number of branches in one branchedmacromonomer molecule is represented by:[Tc−(Tc)^(B)](Mn)^(B)/[Tc−(Tc)^(M)](Mn)^(M).

The range of this value is the same as in the above <2>.

Regarding the “branches” in the macromonomer of the invention, themacromonomer may be subjected to ¹³C-NMR to directly detect the ternarycarbons at the branch points therein, and the number of branches in themacromonomer may be calculated from the thus-detected data. This methodis effective for the branched macromonomer having a relatively largeamount of branches. Measured through ¹³C-NMR, the macromonomer of theinvention has from 0.01 to 40 ternary carbons in one molecule.Preferably, it has from 0.1 to 15 ternary carbons in one molecule. Thecondition in the ¹³C-NMR measurement may be the same as that mentionedhereinabove.

In addition to the above-mentioned requirements for it, the olefinbranched macromonomer of the invention may be such that one and the sameor different two or more types of monomers form the polymer chain at anybranch point therein.

The olefin branched macromonomer of the invention may also be such thatthe stereospecificity of the polymer chain is any of isotactic, atacticor syndiotactic stereospecificity at any branch point therein. Further,it may be such that the copolymerization composition of the polymerchain is the same or different at any branch point therein.

The olefin branched macromonomer [1] of the invention is notspecifically defined so far as it satisfies the above-mentionedrequirements. The constitutive units of the macromonomer may be any ofolefin homopolymers or olefin copolymers, or may also be in any form oftheir combinations. Concretely, atactic polypropylene is represented byAPP; isotactic polypropylene is by IPP; syndiotactic polypropylene is bySPP; and X-g-Y indicates grafting of X with Y. Examples of themacromonomer that comprises homopolymers are APP-g-APP, APP-g-IPP,APP-g-SPP, IPP-g-IPP, IPP-g-SPP, and SPP-g-SPP. In these, vinyl groupsmay be in any of APP, IPP or SPP. Of such macromonomers of homopolymers,preferred are those of propylene (APP, IPP).

Examples of the macromonomer that comprises homopolymers and copolymersare IPP-g-PE, APP-g-PE, SPP-g-PE, in which PE means polyethylene.Copolymers of propylene (P) and ethylene (E) are represented by (P-co-E)in which -co- means copolymerization of the two. Examples of themacromonomer that comprises the copolymer, (P-co-E) are IPP-g-(P-co-E);those in which ethylene (E) is replaced with any of α-olefins havingfrom 4 to 20 carbon atoms, such as butene, hexene and octene, or isreplaced with any of styrene derivatives or cyclic olefins; and those inwhich IPP is replaced with any of APP or SPP. Concretely mentioned arethose with a mark “O” in the following matrix, in which C₄₋₂₀ meansα-olefins having from 4 to 20 carbon atoms; Cyclo and Cy mean cyclicolefins; and St means styrene derivatives.

(B) Side Chain or (A) Main Chain or Side Chains Main Chains P-co-EP-co-C₄₋₂₀ P-co-Cyclo P-co-St IPP 0 0 0 0 APP 0 0 0 0 SPP 0 0 0 0Main chain or Side chains: This means combinations of Main chain (A) andSide chains (B), and combinations of main chain (B) and Side chains (A).

Examples of the macromonomer that comprises copolymers are those with amark “O” in the following matrix.

Main Chain or Side Chains P-co-E P-co-C₄₋₂₀ P-co-Cy P-co-St E-co-C₄₋₂₀E-co-Cy Side Chain P-co-E 0 0 0 0 0 0 or P-co-C₄₋₂₀ 0 0 0 0 0 MainChains P-co-Cy 0 0 0 0 P-co-St 0 0 0 E-co-C₄₋₂₀ 0 0 E-co-Cy 0 P-co-E:propylene-ethylene copolymer P-co-C₄₋₂₀: propylene-C₄₋₂₀ α-olefincopolymer P-co-Cy: propylene-cyclic olefin copolymer P-co-St:propylene-styrene copolymer E-co-C₄₋₂₀: ethylene C₄₋₂₀ α-olefincopolymer E-co-Cy: ethylene-cyclic olefin copolymer Main chain or Sidechains: This means combinations of Main chain (A) and Side chains (B),and combinations of Main chain (B) and Side chains (A).

Of the macromonomers of copolymers mentioned above, especially preferredare the following two.

(1) Olefin branched macromonomers comprising propylene and at least oneselected from ethylene, α-olefins having from 4 to 20 carbon atoms,cyclic olefins and styrenes, and having a propylene content of from 0.1to 99.9 mol %, preferably from 0.2 to 99 mol %, more preferably from 1.0to 95 mol %, even more preferably from 2 to 95 mol %, most preferablyfrom 5 to 90 mol %.

(2) Olefin branched macromonomers comprising ethylene and at least oneselected from α-olefins having from 4 to 20 carbon atoms, cyclic olefinsand styrenes, and having an ethylene content of from 50 to 99.9 mol %,preferably from 60 to 99 mol %.

The olefin in the olefin branched macromonomer of the invention includespropylene, ethylene, α-olefins having from 4 to 20 carbon atoms, cyclicolefins and styrenes.

The α-olefins having from 4 to 20 carbon atoms include, for example,α-olefins such as 1-butene, 3-methyl-1-butene, 4-methyl-1-butene,4-phenyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene,1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 6-phenyl-1-hexene,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene, vinylcyclohexane; and halogen-Concretely,substituted α-olefins such as hexafluoropropene, tetrafluoroethylene,2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene,trifluoroethylene, 3,4-dichloro-1-butene.

The cyclic olefins includes those of the following general formula(I-1):

wherein R^(a) to R¹ each represent a hydrogen atom, a hydrocarbon grouphaving from 1 to 20 carbon atoms, or a halogen-, oxygen- ornitrogen-containing substituent; m indicates an integer of 0 or more;R^(i) and R^(j) each combined with R^(j) and R^(i), respectively, mayform a ring; and R^(a) to R¹ may be the same or different.

In the cyclic olefins of formula (I-1), R_(a) to R¹ each represent ahydrogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, ora halogen-, oxygen- or nitrogen-containing substituent, as so mentionedhereinabove.

Concretely the hydrocarbon group having from 1 to 20 carbon atomsincludes, for example, an alkyl group having from 1 to 20 carbon atomssuch as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyland hexyl groups; an aryl, alkylaryl or arylalkyl group having from 6 to20 carbon atoms such as phenyl, tolyl and benzyl groups; an alkylidenegroup having from 1 to 20 carbon atoms such as methylidene, ethylideneand propylidene groups; and an alkenyl group having from 2 to 20 carbonatoms such as vinyl and allyl groups. However, R^(a), R^(b), R^(e) andR^(f) must not be an alkylene group. In case where any of R^(c), R^(d),R^(g) to R^(l) is an alkylidene group, the carbon atom to which it isbonded does not have any other substituent.

Concretely, the halogen-containing substituent includes, for example, ahalogen atom such as fluorine, chlorine, bromine and iodine atoms; and ahalogen-substituted alkyl group having from 1 to 20 carbon atoms such aschloromethyl, bromomethyl and chloroethyl groups.

The oxygen-containing substituent includes, for example, an alkoxy grouphaving from 1 to 20 carbon atoms such as methoxy, ethoxy, propoxy andphenoxy groups; and an alkoxycarbonyl group having from 1 to 20 carbonatoms such as methoxycarbonyl and ethoxycarbonyl groups.

The nitrogen-containing substituent includes, for example, an alkylaminogroup having from 1 to 20 carbon atoms such as dimethylamino anddiethylamino groups, and a cyano group.

Examples of the cyclic olefins of formula (I-1) are norbornene,5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene,5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene,5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene,5-ethylidenenorbornene, 5-vinylnorbornene,1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,1,2-dihydrocyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene,5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene,5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxynorborneneanhydrate, 5-dimethylaminonorbornene, and 5-cyanonorbornene.

The styrenes for use herein are not specifically defined, but preferredare styrene, alkylstyrenes, and divinylbenzene. More preferred arestyrene, α-methylstyrene, p-methylstyrene and divinylbenzene.

The styrenes include, for example, styrene; alkylstyrenes such asp-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene,p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene,o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene,m-ethylstyrene, m-isopropylstyrene, m-butylstyrene, mesitylstyrene,2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene;alkoxystyrenes such as p-methoxystyrene, o-methoxystyrene,m-methoxystyrene; and halogenostyrenes such as p-chlorostyrene,m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene,o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene,o-methyl-p-fluorostyrene. Further mentioned are trimethylsilylstyrene,vinylbenzoates, and divinylbenzene.

In the invention, one or more of the above-mentioned olefins may be usedeither singly or as combined in any desired manner.

The method for producing the olefin branched macromonomer [1] of theinvention is described in detail hereinunder. For producing the olefinbranched macromonomer [1] of the invention, for example, olefins arehomopolymerized or copolymerized in the presence of a metallocenecatalyst.

The metallocene catalyst includes, for example, transition metalcompounds having one or two ligands of cyclopentadienyl, substitutedcyclopentadienyl, indenyl and substituted indenyl groups, as in JapanesePatent Laid-Open Nos. 19309/1983, 130314/1986, 163088/1991, 300887/1992,211694/1992, and International Patent Publication No. 502036/1989, andthose transition metal compounds in which the ligands are geometricallycontrolled, and these are characterized in that the properties of theiractive points are unified. For the transition metal in these transitionmetal compounds, preferred are those of Group 4 of the Periodic Table,concretely, zirconium, titanium and hafnium. Especially preferred arezirconium and hafnium.

In olefin polymerization or copolymerization in the presence of such ametallocene catalyst, terminal vinyl groups are formed through movementof the β-proton or β-methyl group at the ethylene terminal or propyleneterminal of olefins. Preferably, therefore, the metallocene catalyst foruse in the invention is one that induces the reaction at any of thesetwo sites.

Examples of the metallocene catalyst usable herein arepentamethylcyclopentadienylzirconium trichloride,bis(pentamethylcyclopentadienyl)zirconium dichloride, indenylzirconiumtrichloride, bis(indenyl)zirconium dichloride,dimethylsilylene-bis(indenyl)zirconium dichloride,(dimethylsilylene)(dimethylsilylene)-bis(indenyl)zirconium dichloride,(dimethylsilylene)-bis(2-methyl-4-phenylindenyl)zirconium dichloride,(dimethylsilylene)-bis(benzoindenyl)zirconium dichloride,ethylene-bis(indenyl)zirconium dichloride,(ethylene)(ethylene)-bis(indenyl)zirconium dichloride,(ethylene)(ethylene)-bis(3-methylindenyl)zirconium dichloride,(ethylene)(ethylene)-bis(4,7-dimethylindenyl)zirconium dichloride,(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediylzirconium dichloride,(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconiumdichloride, (methylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediylzirconium dichloride,and compounds derived from them by substituting zirconium therein withany of hafnium or titanium.

A co-catalyst may be used along with the metallocene catalyst. For it,any of those described in the above-mentioned patent publications may beused. Preferred examples of the co-catalyst for use herein are linear orcyclic aluminoxanes (e.g., methylaluminoxane), ionic compounds (e.g.,N,N-dimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetraphenylborate), Lewis acids (e.g., boron compounds such as triphenylborate, tris(pentafluorophenyl) borate), and alkylaluminiums (e.g.,trialkylaluminiums such as triethylaluminium, isobutylaluminium).

Olefin homopolymerization or copolymerization in the presence of thecatalyst as above to give the olefin branched macromonomer of theinvention may be effected in any known manner. For example, it may beeffected in any mode of slurry polymerization, solution polymerization,vapor-phase polymerization, or liquid-phase polymerization in which themonomer of propylene or other α-olefins serves as a medium. In slurrypolymerization, any solvent generally used in ordinary polymerizationmay be used. For example, usable are inert hydrocarbon solvents such aspentane, hexane, heptane, octane, nonane, decane, dodecane, cyclohexane,toluene. Of those, preferred are hexane, heptane, octane and toluene.While polymerized, the molecular weight of the polymer to be producedcan be controlled. For controlling the molecular weight of the polymer,any known method may be employable. In general, the reactiontemperature, the monomer concentration and the catalyst amount arevaried for the molecular weight control. For producing the macromonomerof the invention, employable is any mode of one-stage polymerization ortwo-stage or more multi-stage polymerization.

The olefin to be (co)polymerized into the macromonomer of the inventionincludes propylene, ethylene, α-olefins having from 4 to 20 carbonatoms, cyclic olefins and styrenes. For specific examples of theα-olefins having from 4 to 20 carbon atoms, cyclic olefins and styrenes,referred to are those concretely mentioned hereinabove.

The condition of olefin homopolymerization or copolymerization to givethe macromonomer of the invention is so controlled that the macromonomerproduced has a branched structure and has an increased molecular weight.For example, preferred is low-temperature polymerization at 0° C. orlower, or polymerization for which the monomer concentration isincreased. In general, the reaction temperature is not higher than 0°C., preferably falling between −78 and 0° C.; the reaction pressurefalls between 0.01 and 45 kg/cm² G, preferably between 0.05 ad 40 kg/cm²G. The reaction time may fall between 0.1 an 10 hours. It is effectiveto pre-polymerize the olefins at low temperature under low pressure.Concretely, the olefins are prepolymerized at a temperature fallingbetween −78 and 80° C., preferably between −50 and 60° C., under apressure falling between atmospheric pressure and 10 kg/cm² G,preferably between 0.05 and 5 kg/cm² G, for from 1 minute to 24 hours,preferably from 5 minutes to 12 hours. The degree of prepolymerizationmay fall between 1 and 1000% by weight, preferably between 3 and 800% byweight per gram of the catalyst. The monomer to be used for theprepolymerization may be an α-olefin having 2 or more carbon atoms,preferably propylene.

The polymer product thus obtained is separated from the non-reactedmonomers and the solvent used. Optionally, it may be subjected topost-treatment for deashing, washing and drying.

[2] Olefin Graft Copolymer:

The olefin graft copolymer of the invention is described.

The olefin graft copolymer of the invention is a polymer obtained bycopolymerizing the above-mentioned, olefin branched macromonomer [1]with at least one comonomer selected from ethylene, propylene, α-olefinshaving from 4 to 20 carbon atoms, cyclic olefins and styrenes, in thepresence of a metallocene catalyst or a Ziegler-Natta catalyst,preferably in the presence of a metallocene catalyst.

The metallocene catalyst is described hereinabove. The Ziegler-Nattacatalyst includes, for example, those comprising a transition metalcompound of Group 4 of the Periodic Table and an organoaluminiumcompound (for example, as in Japanese Patent Publication No. 3356/1978);and high-activity Ziegler-Natta catalysts comprising a catalystcomponent obtained through contact of a magnesium compound with atitanium compound in the presence or absence of en electron donor, andan organoaluminium compound (for example, as in Japanese PatentLaid-Open Nos. 43094/1978, 135102/1980, 135103/1980, 18606/1981).

The transition metal compound of Group 4 of the Periodic Table to be inthe Ziegler-Natta catalysts may be a transition metal halide. For it,preferred are titanium halides, and more preferred is titaniumtrichloride. Titanium trichloride may be obtained in various methods.For example, titanium tetrachloride is reduced in any desired manner;the product obtained through the reduction is activated by milling it ina ball mill and/or by washing it with a solvent (for example, in aninert solvent and/or a polar compound-containing inert solvent);titanium trichloride or titanium trichloride eutectoids-(e.g.,TiCl₃+(⅓)AlCl₃) are further co-ground along with any of amines, ethers,esters, sulfur derivatives, halogen derivatives, organic or inorganicnitrogen compounds or phosphorus compounds; or titanium trichloridehaving been liquefied in the presence of an ether compound iscrystallized. In addition, those obtained according to the methoddescribed in Japanese Patent Publication No. 3356/1978 are alsoemployable.

The magnesium compound includes, for example, metal magnesium, magnesiumhalides (e.g., magnesium chloride), and magnesium alkoxides (e.g.,magnesium diethoxide).

The electron donor includes, for example, alcohols (e.g., ethanol) andesters (e.g., benzoates). For the organoaluminium compound serving asthe other component of the catalysts, preferred are compounds of aformula, AlR_(n)X_(3-n), in which R represents an alkyl group havingfrom 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbonatoms, or an aryl group having from 6 to 10 carbon atoms; X represents ahalogen atom; and n is a value satisfying 0<n≦3. Concretely, theyinclude triethylaluminium, triisobutylaluminium, tri-n-propylaluminium,diethylaluminium monochloride, diethylaluminium monobromide,diethylaluminium monoiodide, diethylaluminium monoethoxide,diisobutylaluminium monoisobutoxide, diethylaluminium monohydride,diisobutylaluminium monohydride, ethylaluminium sesquichloride,ethylaluminium dichloride. One or more of these may be used for thecatalyst.

The olefin graft copolymer of the invention is a graft copolymer whichhas branch chains (these may be referred to as side chains) at any ofthe main chain or the side chains (these may be referred to as graftchains). It may have or may not have terminal vinyl groups. Preferably,it has no terminal vinyl group. The olefin graft copolymer of theinvention is not specifically defined in point of the main chain and theside chains, but has the above-mentioned, olefin branched macromonomer[1] at least in any of the main chain or the side chains, and has branchchains (side chains). In case where at least any of the main chain orthe side chains of the olefin graft copolymer is the olefin branchedmacromonomer [1], the others may be a polymer formed throughpolymerization (homopolymerization or copolymerization) of at least onemonomer selected from ethylene, propylene, α-olefins having from 4 to 20carbon atoms, cyclic olefins and styrenes. In this case, the polymer mayhave or may not have branch chains (side chains). When the polymer is acopolymer, the copolymer may be any of random copolymers or blockcopolymers. When the polymer is an ethylene polymer, itsstereospecificity may be any of atactic, isotactic or syndiotacticstereospecificity.

More preferably, the olefin graft copolymer of the invention satisfiesthe following (1) and/or (2):

(1) its intrinsic viscosity [η] measured in a solvent decalin at 135° C.falls between 0.3 and 15 dl/g;

(2) it contains from 0.01 to 70% by weight of the above-mentioned,olefin branched macromonomer.

If the olefin graft copolymer does not satisfy the above (1), or thatis, if its [η] is smaller than 0.3, its mechanical strength is not sogood; but if larger than 15, its workability is often poor. If it doesnot satisfy the above (2), or that is, if the olefin branchedmacromonomer content of the copolymer is smaller than 0.01, the effectof the copolymer to improve the workability of resins will be poor; butif larger than 70, it will lower the flowability of resin melts. Stillmore preferably, the graft copolymer satisfies the following (3) and/or(4):

(3) its intrinsic viscosity [η] measured in a solvent decalin at 135° C.falls between 0.5 and 14 dl/g;

(4) it contains from 0.03 to 70% by weight of the above-mentioned,olefin branched macromonomer.

Even more preferably, the graft copolymer satisfies the following (5)and/or (6):

(5) its intrinsic viscosity [η] measured in a solvent decalin at 135° C.falls between 0.6 and 13 dl/g;

(6) it contains from 0.7 to 65% by weight of the above-mentioned, olefinbranched macromonomer.

Most preferably, the graft copolymer satisfies the following (7) and/or(8):

(7) its intrinsic viscosity [η] measured in a solvent decalin at 135° C.falls between 0.7 and 12 dl/g;

(8) it contains from 0.8 to 60% by weight of the above-mentioned, olefinbranched macromonomer.

One example of producing the olefin graft copolymer of the inventioncomprises preparing a macromonomer to form the side chains of thecopolymer, in the same manner as that for producing the above-mentioned,olefin branched macromonomer [1] (first step), followed bycopolymerizing it with at least one comonomer selected from ethylene,propylene, α-olefins having from 4 to 20 carbon atoms, cyclic olefinsand styrenes, in the presence of a metallocene catalyst or in thepresence of a Ziegler-Natta catalyst (second step). More concretely, themacromonomer component to form the side chains of the copolymer is firstprepared, then this is transferred into a separate polymerizationreactor while the catalytic activity is not still lost, and this iscopolymerized with the comonomer therein. Alternatively, thecopolymerization may be effected in a polymerization reactor thatdiffers from the polymerization reactor in which the side-chain-formingmacromonomer component is prepared through polymerization. In any ofsuch two-stage polymerization (or more multi-stage polymerization) orseparate line polymerization as above, the condition of reactiontemperature and reaction pressure may be the same as that for thepolymerization to prepare the side-chain-forming macromonomer component.For the second stage polymerization in the two-stage polymerizationprocess, a fresh catalyst may be or may not be added to the system afterthe first stage polymerization.

According to the process, obtained are, for example, APP-g-APP,IPP-g-IPP and SPP-g-SPP, for which both the first and second stages ofthe process are for homopolymerization. In the process, when a suitablecatalyst system is selected from metallocene catalysts or Ziegler-Nattacatalysts, various types of graft copolymers can be obtained, including,for example, the above-mentioned graft copolymers of which both the mainchain and the side chains of the macromonomer have the samestereospecificity, and graft copolymers of which the main chain differsfrom the side chains in point of the stereospecificity, such asAPP-g-IPP, APP-g-SPP, IPP-g-SPP. When a combined catalyst systemcomposed of a metallocene catalyst effective for producing APP, IPP andSPP macromonomers and at least one other catalyst is used, it ispossible to produce macromonomers of which the stereospecificity of themain chain differs from that of the side chains. When these steps andcatalysts are combined, various types of olefin graft copolymers such asthose listed in the above-mentioned table can be produced. In theprocess of the invention, the same metallocene catalyst may be used bothin the first step and the second step, or a Ziegler-Natta catalyst maybe used in the second step.

In case where any one of the main chain or the side chains (graftchains) of the olefin graft copolymer of the invention is of a linearpolymer, the olefin graft copolymer of the type can be produced bycopolymerizing a vinyl-terminated linear polymer with at least onecomonomer selected from ethylene, propylene, α-olefins having from 4 to20 carbon atoms, cyclic olefins and styrenes, in the presence of ametallocene catalyst or in the presence of a Ziegler-Natta catalyst. Thevinyl-terminated linear polymer is not specifically defined. For it, forexample, polymers may be modified through exposure to heat or to anyother external energy such as radiations.

The comonomer is selected from ethylene, propylene, α-olefins havingfrom 4 to 20 carbon atoms, cyclic olefins and styrenes, and these may bethe same as those mentioned hereinabove. The above-mentioned metallocenecatalyst or Ziegler-Natta catalyst is used in the process ofcopolymerization. The copolymerization may be effected in the samemanner and under the same condition as those mentioned hereinabove. Inthe invention, one and the same or two or more different types of theabove-mentioned, olefin branched macromonomer [1] may be copolymerizedwith the comonomer, either singly or as combined in any desired ratio.Different types of the macromonomer [1], if combined forcopolymerization, may be blended in a mode of solution blending orpowder blending, or may be directly blended in a reactor. Preferably,the polymerization condition to be employed in the invention is suchthat the resulting copolymer may have a higher molecular weight, forwhich, for example, the monomer concentration is increased.

[3] Olefin Resin Composition:

The olefin resin composition of the invention comprises 100 parts byweight of a thermoplastic resin and from 0.05 to 70 parts by weight ofthe above-mentioned, olefin branched macromonomer [1] or olefin graftcopolymer [2]. Preferably, it comprises 100 parts by weight of athermoplastic resin and from 0.1 to 65 parts by weight, more preferablyfrom 0.2 to 60 parts by weight, even more preferably from 0.3 to 50parts by weight, most preferably from 0.35 to 40 parts by weight of theabove-mentioned, olefin branched macromonomer [1] or olefin graftcopolymer [2]. If the amount of the macromonomer [1] or the copolymer[2] serving as a compatibilizer is smaller than 0.05 parts by weight inthe resin composition, the absolute amount of the compatibilizer is notenough and the compatibilizer will be ineffective for improving thephysical properties of the resin composition. However, if its amount islarger than 70 parts by weight, the olefin branched macromonomer [1] orthe olefin graft copolymer [2] is to be the main ingredient of the resincomposition, and, if so, the macromonomer [1] or the copolymer [2] couldnot serve as a compatibilizer in the resin composition. In the olefinresin composition of the invention, any of the olefin branchedmacromonomer [1] or the olefin graft copolymer [2] may be used.Preferably, however, the resin composition contains the olefin graftcopolymer [2].

The thermoplastic resin to be in the resin composition includes, forexample, polyolefin resins, polystyrene resins, condensed polymershaving an increased molecular weight, and polymers produced throughaddition polymerization and having an increased molecular weight.Examples of the polyolefin resins are high-density polyethylene,low-density polyethylene, poly-3-methylbutene-1, poly-4-methylpentene-1;linear low-density polyethylene copolymerized with any of butene-1,hexene-1, octene-1,4-methylpentene-1, or 3-methylbutene-1;ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetatecopolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer,ethylene ionomer, and polypropylene. Examples of the polystyrene resinsare general polystyrene, isotactic polystyrene, and high-impactpolystyrene (modified with rubber). Examples of the condensed polymershaving an increased molecular weight are polyacetal resin, polycarbonateresin; polyamide resin such as nylon 6 and nylon 6; polyester resin suchas polyethylene terephthalate and polybutylene terephthalate;polyphenylene-oxide resin, polyimide resin, polysulfone resin,polyether-sulfone resin, and polyphenylene-sulfide resin. Examples ofthe polymers produced through addition polymerization and having anincreased molecular weight are polymers of polar vinyl monomers, andpolymers of diene monomers, concretely, polymethyl methacrylate,polyacrylonitrile, acrylonitrile-butadiene copolymer,acrylonitrile-butadiene-styrene copolymer, diene polymer in which thediene chain is hydrogenated, and thermoplastic elastomer.

In the olefin resin composition of the invention, one preferredcombination of thermoplastic resins is a polyolefin—polyolefincombination. For example, it includes a combination of polypropylene andpolyethylene such as LLDPE, LDPE or HDPE; a combination of polypropyleneand a soft olefin polymer such as ethylene/propylene copolymer,thermoplastic elastomer, EPDM or EPR; a combination of polypropylene andpolystyrene such as APS, IPS or SPS; a combination of polypropylene andpropylene/α-olefin copolymer; a combination of polyethylene andpolystyrene such as APS, IPS or SPS; a combination of polyethylene andethylene/α-olefin copolymer; a combination of propylene/α-olefincopolymer and polystyrene such as APS, IPS or SPS; a combination ofethylene/α-olefin copolymer and polystyrene such as APS, IPS or SPS; acombination of ethylene/styrene copolymer and polypropylene resin; acombination of ethylene/styrene copolymer and polyethylene resin; and acombination of polyethylene and a soft olefin polymer such asethylene/propylene copolymer, elastic elastomer, EPDM or EPR. To thecomposite resin system as above, added is the olefin branchedmacromonomer [1] or the olefin graft copolymer [2] serving as acompatibilizer, and the mechanical properties of the resulting resincomposition are improved.

Preferably, the olefin resin composition of the invention is such thatthe relaxation rate of the long-term relaxation component therein,measured through solid ¹H-NMR, (1/R₁) falls between 1.0 and 2.0 (1/sec),more preferably between 1.2 and 1.8 (1/sec), even more preferablybetween 1.3 and 1.6 (1/sec). Also preferably, the olefin resincomposition of the invention is such that the ratio of the relaxationrate (1/R₁) to the relaxation rate (1/R₁)₀ of the long-term relaxationcomponent, measured through solid ¹H-NMR, of a resin composition notcontaining the propylene branched macromonomer, [(1/R₁)/(1/R₁)₀],satisfies the following relationship:[(1/R₂)/(1/R ₁)₀]≧1.01.Satisfying it, the resin compatibility in the composition is good.More preferably, the ratio satisfies;[(1/R ₁)/(1/R ₁)₀]≧1.02,even more preferably,[(1/R ₁)/(1/R ₁)₀]≧1.03.

In the invention, the values (1/R₁) and (1/R₁)₀ of the resincompositions are measured according to a method of inversion recovery(180°−τ−90°, pulse process), using a solid ¹H-NMR device mentionedbelow.

-   -   Device: BRUKER's CPX-90    -   Nucleus to be measured: hydrogen nucleus (¹H)

-   Frequency: 90 MHz

-   Temperature: 30° C.

-   90° pulse width: 2.4 to 2.5 microseconds

The invention is described in more detail with reference to thefollowing Examples, which, however, are not intended to restrict thescope of the invention.

EXAMPLE I-1 Production of Propylene Branched Macromonomer

<1> Production of Branched Propylene Macromonomer:

A 1.6-liter, stainless pressure autoclave was well dried, and 100 ml ofdewatered toluene and 6 mmols of Toso-Akuzo's methylaluminoxane were putinto it in a nitrogen atmosphere, and these were cooled to 0° C. Withstirring them, propylene was introduced into the autoclave, and itspressure was increased up to 5.0 kg/cm² G. The autoclave was thussaturated with propylene, and introducing propylene thereinto wasstopped. Then, 1 ml of a toluene solution of 10 μmols ofbis(pentamethylcyclopentadienyl) zirconium dichloride was put into theautoclave to start the polymerization of the monomer, propylene. Thereaction temperature was kept at −5° C., and the polymerization wascontinued for 8 hours. After the polymerization finished, thenon-reacted propylene was degassed and removed. The reaction mixture wasput into a large amount of methanol and the polymer was recovered. Thiswas dried at 80° C. for 12 hours under reduced pressure, and the amountof the polymer thus obtained was 20.1 g.

<2> Evaluation of branched propylene macromonomer:

The weight-average molecular weight (Mw), the ratio of temperaturedependency of solution viscosity (E₂/E₁), and the terminal vinylselectivity of the polymer obtained in the above were measured accordingto the methods mentioned hereinabove. The results obtained are shown inTable I-1.

In the Table, Example 1 means Example I-1, and the same shall apply tothe other Examples and Comparative Examples.

COMPARATIVE EXAMPLE I-1 Production of Linear Propylene Macromonomer

The same process as in Example I-1 was repeated, except that the amountof toluene used was 400 ml, bis(pentamethylcyclopentadienyl)zirconiumdichloride was replaced with cyclopentadienylzirconium dichloride, thepolymerization temperature was 20° C., and the polymerization time was90 minutes. As a result, 15.4 g of a polymer was obtained herein. Thiswas evaluated in the same manner as in Example I-1, and its data aregiven in Table I-1.

TABLE I-1 Details Example 1 Co. Example 1 Resin Properties structurebranched APP linear APP Mw 7800 7900 Terminal Vinyl 91.5 0 Selectivity(%) Intrinsic Viscosity [η] (g/dl) 0.105 0.100 Relative Viscosity (75°C.) 3.18 3.20 Sample Concentration (g/dl) 14.02 05.39 E1 — 3.36 × 10⁵ E24.09 × 10⁵ — E2/E1 1.22 —

EXAMPLE I-2 Production of Propylene Branched Macromonomer

(1) Synthesis of Side-chain-forming Propylene Oligomer:

A 1.6-liter, stainless pressure autoclave was well dried, and 400 ml ofdewatered toluene, 6 mmols (in terms of aluminium equivalent) ofToso-Akuzo's methylaluminoxane and 10 μmols ofbis(pentamethylcyclopentadienyl)hafnium dichloride were put into it in anitrogen atmosphere, and these were heated up to 30° C. Propylene havinga controlled partial pressure of 6 kg/cm² G was continuously introducedinto it, and reacted for 4 hours. The non-reacted propylene was degassedand remove, and the reaction mixture was recovered. This was washed withan aqueous solution of 3 N HCl, and then well washed with water. Thiswas dried with anhydrous sodium sulfate, and subjected to distillationto remove the component having a boiling point at normal pressure of nothigher than 230° C. Thus was obtained a viscous substance. This is anoligomer, atactic polypropylene (APP). Its NMR analysis revealed thatthe oligomer was vinyl-terminated.

This was dissolved in hexane, and dewatered and purified throughbubbling with nitrogen.

(2) Production of propylene branched macromonomer:

A 1.6-liter, stainless pressure autoclave was well dried. 400 ml ofdewatered toluene, 100 ml of a heptane solution of 15 g of the propyleneoligomer produced in the above (1), 0.5 mmols of triisobutylaluminium,and 6 mmols (in terms of aluminium equivalent) of Toso-Akuzo'smethylaluminoxane were put into it in a nitrogen atmosphere, and stirredfor 10 minutes at room temperature. To this was added 10 μmols ofrac-(1,2-ethylene)(2,1-ethylene)-bis(indenyl)hafnium dichloride[Et₂Ind₂HfCl₂]. This was heated up to 50° C., and propylene wascontinuously introduced thereinto to have a controlled partial pressureof 3 kg/cm² G, and polymerized for 4 hours.

After the polymerization, the reaction mixture was put into a largeamount of methanol, and the polymer component was recovered. This wasdried in air for one full day. To remove the non-reacted propyleneoligomer (1) from it, this was washed five times with 500 ml of hexane.The insoluble product was dried, and 35 g of propylene branchedmacromonomer was obtained.

(3) Evaluation of Propylene Branched Macromonomer:

The propylene branched macromonomer obtained in the above (2) wasevaluated as follows:

<1> Weight-average molecular weight (Mw);

This was measured through GPC according to the method mentioned above,and its Mw was 18400.

<2> Vinyl Content:

This was analyzed through ¹H-NMR in the manner mentioned above. Based onthe ratio of the methyl proton of the vinyl group appearing at 4.8 to5.1 ppm to the unsaturated bonds appearing at 4 to 6 ppm, the ratio ofthe vinyl group to all the unsaturated bonds in the macromonomer wascalculated, and it was 89.2%.

<3> Branch analysis:

The macromonomer was analyzed for its branches in the manner as follows:The side-chain-forming propylene oligomer, or that is, thevinyl-terminated atactic polypropylene [1] prepared in the above (1);the propylene branched macromonomer [II], which is a vinyl-terminatedcopolymer composed of [I] and propylene; and a control, polypropylene[III] produced not using the side-chain-forming propylene oligomer wereanalyzed through NMR. It revealed that the meso-triad fraction (mm) of[I], [II] and [III] is 23%, 45% and 85%, respectively. GPC analysis of[I] and [II] revealed that Mn of [I] is 4500 and Mn of [II] is 18400.The number of branches in one macromonomer molecule, calculatedaccording to the stereospecificity analysis <3> mentioned above, is 2.6.The data obtained are shown in Table I-2.

EXAMPLE I-3 Production of Propylene/ethylene Branched Macromonomer

(1) Continuous polymerization:

A 1.6-liter, stainless pressure autoclave was well dried. 600 ml ofdewatered toluene, and 6 mmols (in terms of aluminium equivalent) ofToso-Akuzo's methylaluminoxane were put into it in a nitrogenatmosphere. Its temperature was kept at 20° C. This was saturated withpropylene having a controlled partial pressure of 7 kg/cm² G and withethylene having a controlled partial pressure of 2 kg/cm² G. Through acatalyst line, 10 μmols of bis (pentamethylcyclopentadienyl)hafniumdichloride was put into it, and the monomers were copolymerized for 5minutes. In this stage, the inner pressure decreased owing to themonomer polymerization. Immediately after the reaction, the non-reactedmonomers were degassed and removed, and they were completely removedthrough bubbling with nitrogen. A part of the toluene solution of thereaction mixture, propylene/ethylene copolymer [1] was sampled foranalysis of the copolymer in this stage. Next, this was kept at 30° C.,and propylene was continuously fed thereinto, having a controlledpartial pressure of 6 kg/cm² G, and polymerized for 240 minutes. Afterthe reaction, the reaction mixture was put into a large amount ofmethanol, and repeatedly washed with methanol to remove the propyleneoligomer. This was dried, and 45 g of propylene/ethylene branchedmacromonomer [II] was obtained.

(2) Evaluation of Propylene/ethylene Branched Macromonomer:

The propylene/ethylene branched macromonomer obtained in the above (1)was evaluated as follows:

<1> The macromonomer was analyzed in the same manner as in Example I-2,and its Mw and vinyl selectivity were 15400 and 87%, respectively.

<2> Branch analysis:

The macromonomer was analyzed for its branches, according to the methodof composition analysis <2> mentioned hereinabove.

Concretely, the side-chain-forming propylene/ethylene copolymer [I](this was sampled in the course of macromonomer production), and thepropylene/ethylene branched macromonomer [II] were analyzed through NMRand GPC. This revealed that the ethylene content of [I] and [II] is 56mol % and 8 mol %, respectively. The GPC analysis revealed that themolecular weight at the peak tops of [I] and [II] is 5600 and 15400,respectively. From the data, the number of branches in one macromonomermolecule is 0.40. The data obtained are shown in Table I-2.

EXAMPLE I-4 Production of Propylene/ethylene Branched Macromonomer

(1) One-pot polymerization for producing branched macromonomer:

A 1.6-liter, stainless pressure autoclave was well dried: 600 ml ofdewatered toluene, and 6 mmols (in terms of aluminium equivalent) ofToso-Akuzo's methylaluminoxane were put into it in a nitrogenatmosphere. Its temperature was kept at 20° C. This was saturated withpropylene having a controlled partial pressure of 7 kg/cm² G and withethylene having a controlled partial pressure of 2 kg/cm² G. Through acatalyst line, 10 μmols of bis (pentamethylcyclopentadienyl)hafniumdichloride was put into it, and the monomers were copolymerized for 5minutes. In this stage, the inner pressure decreased owing to themonomer polymerization. Immediately after the reaction, the non-reactedmonomers were degassed and removed, and they were completely removedthrough bubbling with nitrogen. A part of the toluene solution of thereaction mixture, propylene/ethylene copolymer [1] was sampled foranalysis of the copolymer in this stage. Next, this was kept at 30° C.,and propylene at a flow rate of 10 normal liters/min and ethylene at aflow rate of 2 normal liters/min were continuously fed thereinto, havinga controlled total pressure of 7 kg/cm² G, and polymerized for 60minutes. After the reaction, the reaction mixture containingtoluene-insoluble substances was put into a large amount of methanol,and repeatedly washed with methanol Then, this was dried in air for onefull day. The yield of the reaction mixture [II] was 165 g. To removethe non-reacted ethylene/propylene oligomer from it, this was washedfive times with 500 ml of toluene. The remaining insoluble solid wasdried, and 145 g of ethylene/propylene branched macromonomer [III] wasobtained.

(2) Evaluation of Propylene/ethylene Branched Macromonomer

<1> Weight-average Molecular Weight (Mw) and Vinyl Content:

The molecular weight and the vinyl selectivity of the macromonomer were75000 and 95.8%, respectively.

<2> Branch Analysis:

The macromonomer was analyzed for its branches, according toabove-mentioned method of GPC <1>.

Concretely, the propylene/ethylene copolymer [I] (this was sampled inthe course of macromonomer production), the ethylene/propylene branchedmacromonomer mixture [II], and the ethylene/propylene branchedmacromonomer [III] were analyzed through GPC. This revealed that themolecular weight at the peak tops of [I] and [III] is 5600(corresponding to (Mn)^(M)) and 75000 (corresponding to (Mn)^(B)),respectively. From the data of [II], the existence ratio, a, of thenon-reacted oligomer (this is to form the side chains in the branchedmacromonomer, but is not reacted to form them) is 19.1%.

The amount, b, of the side-chain-forming oligomer fed to thepolymerization system (this is derived from the data of the sample ofthe propylene/ethylene copolymer [I]) is 33 g. The yield, c, of thereaction mixture that contains the branched macromonomer is 165 g. Fromthese values, the number of branches in one macromonomer molecule is0.15. The data obtained herein are shown in Table I-2.

EXAMPLE I-5 Production of Ethylene/propylene Branched Macromonomer

(1) Continuous polymerization:

A 1.6-liter, stainless pressure autoclave was well dried. 600 ml ofdewatered toluene, and 6 mmols (in terms of aluminium equivalent) ofToso-Akuzo 's methylaluminoxane were put into it in a nitrogenatmosphere. Its temperature was kept at 20° C. This was saturated withpropylene having a controlled partial pressure of 7 kg/cm² G and withethylene having a controlled partial pressure of 2 kg/cm² G. Through acatalyst line, 10 μmols of bis (pentamethylcyclopentadienyl) hafniumdichloride was put into it, and the monomers were copolymerized for 5minutes. In this stage, the inner pressure decreased owing to themonomer polymerization. Immediately after the reaction, the non-reactedmonomers were degassed and removed, and they were completely removedthrough bubbling with nitrogen. The reaction-mixture was put into alarge amount of methanol and washed with it, and the methanol-insolubleviscous substance was recovered. This was dried under reduced pressure.After dried, this was re-dissolved in hexane, and dewatered throughbubbling with nitrogen.

(2) Copolymerization of Ethylene/propylene Oligomer and Propylene:

A 1.6-liter, stainless pressure autoclave was well dried. 400 ml ofdewatered toluene, 100 ml of a toluene solution of 15 g of thepropylene/ethylene oligomer [I] produced in the above (1), 0.5 mmols oftriisobutylaluminium, and 6 mmols (in terms of aluminium equivalent) ofToso-Akuzo's methylaluminoxane were put into it in a nitrogenatmosphere, and stirred for 10 minutes at room temperature. To this wasadded 10 μmols of rac-(1,2-ethylene)(2,1-ethylene)-bis(indenyl)hafniumdichloride [Et₂Ind₂HfCl₂]. This was heated up to 40° C., and propylenewas continuously introduced thereinto to have a controlled partialpressure of 3 kg/cm² G, and polymerized for 15 hours.

After the polymerization, the reaction mixture was put into a largeamount of methanol, and the polymer component was recovered. This wasdried in air for one full day. To remove the non-reacted macromonomerfrom it, this was washed five times with 500 ml of hexane. The insolubleproduct was dried, and 60 g of propylene branched macromonomer [II] wasobtained.

(3) Evaluation of branched ethylene/propylene macromonomer:

<1> The molecular weight and the vinyl selectivity of the macromonomerwere 12500 and 88.7%, respectively.

<2> Branch analysis:

The macromonomer was analyzed for its branches, according to the methodof composition analysis <2> mentioned hereinabove.

Concretely, the propylene/ethylene macromonomer [I] and thepropylene/ethylene branched macromonomer [II] were analyzed through NMRand GPC. This revealed that the ethylene content of [I] and [II] is 56mol % and 5 mol %, respectively. The GPC analysis revealed that themolecular weight at the peak tops of [I] and [II] is 5600 and 12500,respectively. From the data, the number of branches in one macromonomermolecule is 0.20. The data obtained are shown in Table I-2.

TABLE I-2 Details Example 1 Example 2 Example 3 Example 4 Example 5Resin Properties Terminal Vinyl Selectivity (%) 91.5 89.2 87.0 95.8 88.7Mw 7800 18400 15400 75000 12500 Structure APP IPP-g-APP APP-g-EP EP-g-EPIPP-g-EP Branch Content (mol %) — 5.0 — — — Number of Branches(/molecule) — 0.11 2.5 0.15 0.6 Propylene Content (mol %) 100 100 92 7295

EXAMPLE I-6 Production of Graft Polymer

8 g of the macromonomer produced in Example I-1 was dissolved in 400 mlof toluene, and bubbled with nitrogen for 5 hours to thereby attaincomplete oxygen removal and water removal from it. A 1.6-liter stainlesspressure autoclave was fully dried, and all of the toluene solution ofthe dried macromonomer and 50 ml of additional dry toluene were put intoit in a nitrogen atmosphere to make 400 ml in all therein. 0.5 mmols oftriisobutylaluminium, and 5 mmols of Toso-Akuzo's methylaluminoxane wereadded to it, heated up to 40° C., and kept stirred for 10 minutes at thetemperature. To this was added 0.5 ml of a toluene solution of 1.0 μmolof racemi-dimethylsilyl-bis[2-methyl-4-phenylindenyl]zirconiumdichloride. Next, propylene was introduced thereinto to have 3 anincreased pressure of 2.0 kg/cm² G, and polymerized for 25 minutes.After the polymerization, the non-reacted monomer was degassed andremoved, and the reaction mixture was put into a large amount ofmethanol. This was filtered to recover the polymer. The polymer waswashed three times with hexane to remove the non-reacted macromonomerfrom it. This was filtered and dried under reduced pressure. The yieldof the graft copolymer thus obtained was 120 g.

Its intrinsic viscosity was 2.02 dl/g, and its macromonomer contentmeasured through ¹H-NMR was 0.8% by weight.

EXAMPLE I-7 Production of Graft Polymer

In the same manner as in Example I-6 using 1.0 μmol ofracemi-dimethylsilyl-bis[2-methyl-4-phenylindenyl]zirconium dichloride,obtained was an ethylene graft copolymer, for which, however, propylenewas replaced by ethylene, the polymerization pressure was 1.0 kg/cm² G,the polymerization temperature was 60° C., and the polymerization timewas 17 minutes. The yield of the graft copolymer obtained was 36.6 g,the intrinsic viscosity thereof was 1.63 dl/g, and the macromonomercontent thereof measured through ¹H-NMR was 1.2% by weight.

EXAMPLE I-8 Production of Olefin Resin Composition

(1) Preparation of Thermoplastic Resins and Properties Thereof:

For use herein, PP was prepared in the following manner.

The same pressure autoclave as in Example I-1 was used. 400 ml of asolvent, dewatered heptane, 0.7 mmols of triisobutylaluminium, and 5μmols (in terms of Zr) of a catalyst rac-Me₂Si-[2Me-4Ph-Ind]₂ZrCl₂ heldon a solid co-catalyst SiO₂/MAO (methylaluminoxane) were put into theautoclave. In the catalyst used, the ratio of MAO/Zr is 400 by mol, andthe ratio of SiO₂/MAO is 2.76/1 by weight.

After the catalyst was put into the autoclave, propylene was introducedthereinto to have a controlled pressure of 5 kg/cm² G, and waspolymerized at 60° C. for 120 minutes. 150 g of polypropylene was thusobtained. Its intrinsic viscosity was 2.76 dl/g, and its melting pointwas 148° C.

Also for use herein, APP was prepared in the following manner:

A 5-liter stainless pressure autoclave was fully dried. 3 liters ofdewatered toluene, 2 mmols of triisobutylaluminium, and 15 ml ofToso-Akuzo's methylaluminoxane were put into it in a nitrogenatmosphere. This was kept stirred for 10 minutes. 15 μmols of(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediylzirconiumdichloride [Cp*(CH₂)₂(tBuN)TiCl₂] was added thereto, and propylene wasintroduced into it to have an increased pressure of 7.5 kg/cm² G, andpolymerized at 50° C. for 45 minutes. After the polymerization, thenon-reacted monomer was degassed and removed. The reaction mixture wasput into a large amount of methanol, and polypropylene was recovered.This was then dried at 80° C. under reduced pressure for 12 hours. Theyield of polypropylene thus obtained was 470 g. Its intrinsic viscositywas 3.10 dl/g. This showed no melting point in DSC, and this wasidentified as atactic polypropylene (APP) by NMR.

(2) Preparation of Olefin Resin Composition:

The above PP and APP, amounting 100 parts by weight in total, and 5parts by weight of the polymer obtained in Example I-6 were added toxylene containing 4000 ppm of an antioxidant, BHT, and dissolved thereinunder heat. This was re-precipitated in a large amount of methanol, andthen dried to prepare an olefin resin composition.

(3) Evaluation of Olefin Resin Composition:

In a solvent decalin at 135° C., the intrinsic viscosity [η] of theolefin resin composition was measured, and corrected according to theHuggins' viscosity equation in which the Huggins' constant is 0.35.

The relaxation rate of the long-term relaxation component of the resincomposition, (1/R₁) and (1/R₁)₀, was measured according to a method ofinversion recovery (180°-τ-90°, pulse process), using a solid ¹H-NMRdevice mentioned below. The data obtained are shown in Table I-3.

-   -   Device: BRUKER's CPX-90    -   Nucleus to be measured: hydrogen nucleus (¹H)    -   Frequency: 90 MHz    -   Temperature: 30° C.    -   90° pulse width: 2.4 to 2.5 microseconds

Measured through DSC and solid ¹H-NMR (solid echo process), the degreeof crystallization was the same between PP and HDPE.

COMPARATIVE EXAMPLE I-2

The same process as in Example I-8 was repeated herein, in which,however, the polymer obtained in Example I-6 was not used. The dataobtained are shown in Table I-3.

EXAMPLE I-9

The same process as in Example I-8 was repeated herein, in which,however, PP was replaced with HDPE (Idemitsu Petrochemical's 440M) andthe polymer of Example I-6 was with that of Example I-7. The dataobtained are shown in Table I-3.

COMPARATIVE EXAMPLE I-3

The same process as in Example I-9 was repeated herein, in which,however, the polymer of Example I-7 was not used. The data obtained areshown in Table I-3.

TABLE I-3 Comp. Details Example 8 Ex. 2 Example 9 Comp. Ex. 3 PP (wt. %)90 90 — — HDPE (wt. %) — — 90 90 APP (wt. %) 10 10 10 10 Polymer ofExample 6 5 — — — (wt. pts.) Polymer of Example 1 — — 5 — (wt. pts.)Relaxation Rate (1/R₁) 1.45 — 1.66 — Relaxation Rate (1/R₁)₀ — 1.40 —1.52 [(1/R₁)/(1/R₁)₀] 1.04 — 1.09 —

EXAMPLE I-10 Production of Graft Copolymer

(1) Preparation of Aluminoxane:

For use herein, methylaluminoxane was processed in the following manner.

1.0 liter of a toluene solution of methylaluminoxane (1.5 mols/liter,from ALBEMARLE, containing 14.5% by weight of trimethylaluminium) wasvaporized under reduced pressure (10 mmHg) at 60° C. to remove thesolvent, and then dried up. In this condition, this was kept as it wasfor 4 hours, and then cooled to room temperature to obtain dry-upmethylaluminoxane. The dry-up methylaluminoxane was re-dissolved indewatered toluene added thereto, to thereby restore its volume to theoriginal before solvent removal. Then, the trimethylaluminium content ofthe methylaluminoxane solution was determined through ¹H-NMR, and was3.6% by weight. The total aluminium content of the methylaluminoxanesolution was measured according to a fluorescent X-ray (ICP) method, andwas 1.32 mols/liter. Then, the solution was statically left as it wasfor 2 full days to thereby make the insoluble component depositedtherein. The supernatant was filtered through a G5 glass filter in anitrogen atmosphere to recover the filtrate. This is methylaluminoxane(a) for use herein. Its concentration measured through ICP was 1.06.From the thus-processed methylaluminoxane, 10.9% by weight oforganoaluminium and 17.3% by weight of the insoluble component wereremoved.

(2) Preparation of Carrier for Olefin Polymerization Catalyst:

27.1 g of SiO₂ (Fuji Silicia Chemical's P-10) was dried under reducedpressure at 200° C. for 4.0 hours in a slight nitrogen atmosphere, and25.9 g of dry SiO₂ was obtained. The dry SiO₂ was put into 400 ml ofdewatered toluene that had been previously cooled to −78° C. in a bathof dry ice/methanol, and stirred. With still stirring, 145.5 ml of atoluene solution of the methylaluminoxane (a) prepared in the above (1)was dropwise added to the toluene suspension of SiO₂, over a period of 2hours all through a dropping funnel.

Next, this was stirred for 4.0 hours, and then warmed from −78° C. up to20° C. over a period of 6 hours, and this was kept in this condition for4.0 hours. Next, this was heated from 20° C. up to 80° C. over a periodof 1 hour, and then left at 80° C. for 4.0 hours to thereby complete thereaction of silica and methylaluminoxane therein. The resultingsuspension was filtered at 80° C., and the solid thus obtained waswashed twice with 400 ml of dewatered toluene at 60° C. and then twicewith 400 ml of dewatered n-heptane at 60° C. After thus washed, thesolid was dried under reduced pressure at 60° C. for 4.0 hours, and33.69 g of SiO₂-held methylaluminoxane was obtained. This serves as acarrier for olefin polymerization catalyst. The proportion ofmethylaluminoxane held on SiO₂ was 30.1% per gram of SiO₂.

To all the thus-obtained, SiO₂-held methylaluminoxane, added wasdewatered n-heptane to make 500 ml. The methylaluminoxane concentrationin the suspension thus obtained herein was 0.27 mols/liter.

(3) Preparation of Catalyst Component:

2.0 mmols (7.41 ml) of the SiO₂-held methylaluminoxane prepared in theabove (2) was put into a 50-ml container that had been purged with drynitrogen, to which was added 20 ml of dewatered toluene and stirred. Tothe resulting suspension, added was 1.0 ml (10 μmols) of a toluenesolution ofracemi-dimethylsilyldiylbis-2-methyl-4-phenylindenylzirconium dichloride(mol/ml), and kept stirred at room temperature for 0.5 hours. Stirringit was stopped, and the solid catalyst component was deposited. Thethus-deposited solid catalyst component was found red and the solutionwas colorless transparent. The solution was removed through decantation,20 ml of n-heptane was added to the residue, and an SiO₂-heldmetallocene catalyst slurry was thus obtained.

(4) Production of Graft Copolymer:

200 ml of a heptane solution of the macromonomer prepared in Example I-3(1) (this solution was prepared by dissolving 10 g of the macromonomerin heptane, and then well bubbled with nitrogen to fully remove waterand oxygen from it), 0.5 mmols of triisobutylaluminium (TIBA), and 5μmols (in terms of zirconium) of the carrier-held catalyst that had beenprepared in the above (1) were put into a 1.6-liter stainless pressureautoclave equipped with a stirrer, in a nitrogen atmosphere. These werestirred, and heated up to 60° C. Propylene was introduced into it for120 minutes to have a pressure of 0.6 MPa (gauge), and polymerized toproduce a polymer.

After the reaction, the autoclave was degassed and opened, and thereaction mixture was taken out and filtered to recover the graftcopolymer. This was washed repeatedly four times with a large amount ofheptane to remove the non-reacted macromonomer. The thus-washed graftcopolymer was dried under reduced pressure at 80° C. for 6 hours. Theyield of the thus-dried graft copolymer was 42 g. Its intrinsicviscosity [η] was 2.20 dl/g, and the number of branches in the copolymerwas 0.2/molecule.

EXAMPLE I-11 Production of Olefin Resin Composition

(1) Production of Low-Stereospecificity Polypropylene:

<1> Preparation of Magnesium Compound:

A glass reactor having a capacity of about 6 liters and equipped with astirrer was fully purged with nitrogen gas. About 2430 g of ethanol, 16g of iodine and 160 g of metal magnesium were put into it, heated withstirring, and reacted under reflux until no hydrogen gas went out of thesystem, to thereby form a solid reaction product. The reaction liquidcontaining the solid product was dried under reduced pressure, and amagnesium compound was thus obtained.

<2> Preparation of Solid Catalyst Component (A):

16 g of the magnesium compound obtained in the above <1>, 80 ml of pureheptane, 2.4 ml of silicon tetrachloride, and 2.3 ml of diethylphthalate were put into a 0.5-liter, three-neck glass flask that hadbeen fully purged with nitrogen gas. This was kept at 90° C., and 77 mlof titanium tetrachloride was added thereto with stirring, and reactedat 110° C. for 2 hours. Then, the solid component was separated from it,and washed with pure heptane at 80° C. 122 ml of titanium tetrachloridewas further added thereto, reacted at 110° C. for 2 hours, and thenfully washed with pure heptane. Thus was obtained a solid catalystcomponent (A).

<3> Production of Low-stereospecificity Polypropylene:

20 g of polypropylene powder, 5.0 mmols of triisobutylaluminium (TIBA),0.125 mmols of 1-allyl-3,4-dimethoxybenzene (ADMB), 0.2 mmols ofdiphenyldimethoxysilane (DPDMS), and 20 ml of a heptane solutioncontaining 0.05 mmols (in terms of titanium) of the solid catalystcomponent (A) obtained in the above <2> were put into a 5-liter,stainless pressure autoclave, and this was degassed for 5 minutes. Then,propylene was introduced into it to have a total pressure of 2.8 MPa·G,and polymerized at 70° C. for 1.7 hours in a mode of vapor-phasepolymerization.

<4> Properties of Polypropylene:

The polypropylene obtained in the above <3> is a soft polypropylenehaving the following properties:

-   (i) boiling heptane-insoluble content: 62.4% by weight,-   (ii) intrinsic viscosity [η] in a solvent decalin at 135° C.: 4.27    dl/g,-   (iii) structure: composition of isotactic polypropylene and atactic    polypropylene.    (2) Preparation of Olefin Resin Composition:

An olefin resin composition was prepared in the same manner as inExample I-8 (2), for which, however, used were 100 parts by weight ofthe low-stereospecificity polypropylene obtained in the above (1) and 3parts by weight of the graft copolymer obtained in Example I-10.

(3) Evaluation of Olefin Resin Composition:

The relaxation rate of the olefin resin composition was determined inthe same manner as in Example I-8 (3). The data are shown in Table I-4.

EXAMPLE I-12 Production of Olefin Resin Composition:

(1) Production of High-rubber Block Copolymer:

<1> Production of Catalyst through Prepolymerization:

48 g of the solid catalyst component (A) prepared in Example I-11 (1)<2>was put into a nitrogen-purged, 1-liter three-neck flask equipped with astirrer. 400 ml of dewatered heptane was added thereto. This was heatedup to 40° C., and 2 mmols of triethylaluminium and 6.3 ml ofdicyclopentyldimethoxysilane were added thereto. Propylene gas wasintroduced into this under ordinary pressure, and reacted with it for 2hours. The solid component was fully washed with dewatered heptane. Thisis a solid catalyst (B).

<2> Production of High-rubber Block Polypropylene:

A 5-liter stainless autoclave equipped with a stirrer was fully purgedwith nitrogen gas, then dried, and thereafter purged with propylene gas.This was kept at 70° C., and propylene gas was introduced into it tohave an increased pressure of 0.05 MPaG. In this condition, hydrogen gaswas introduced into it to have a partial pressure of 0.9 MPaG, andpropylene gas was gradually introduced thereinto to have a furtherincreased pressure of 2.8 MPaG. Apart from this, 20 ml of heptane, 4mmols of triethylaluminium, 1 mmol of dicyclopentyldimethoxysilane, and0.02 mmols of the solid catalyst (B) were put into a 60-ml catalystsupply tube that had been purged with nitrogen gas, and these were ledinto the autoclave through the tube. In the autoclave containing them,propylene was polymerized for 60 minutes into a propylene homopolymer.

Next, the autoclave was degassed to atmospheric pressure, and thehomopolymer therein was sampled in a nitrogen atmosphere. The sample isfor measuring its intrinsic viscosity [η].

Next, the autoclave was degassed to vacuum, and ethylene/propylene gasin a ratio of 1:1 by mol was introduced thereinto to have an increasedpressure of 1.5 MPaG, and copolymerized at 70° C. for 65 minutes. Duringthe copolymerization, the pressure and the monomer flow rate were keptconstant. After this, the autoclave was degassed and cooled to roomtemperature, and the polymer powder was taken out.

Its copolymer moiety formed in the second-stage polymerization was 42.6%by weight.

The intrinsic viscosity of the homopolymer moiety of the block copolymerwas 1.0 dl/g; and that of the copolymer moiety thereof was 4.8 dl/g.

(2) Preparation of Olefin Resin Composition:

An olefin resin composition was prepared in the same manner as inExample I-6 (2), for which, however, used were 100 parts by weight ofthe high-rubber block polypropylene obtained in the above (1) and 5parts by weight of the graft copolymer obtained in Example I-10.

(3) Evaluation of Olefin Resin Composition:

The relaxation rate of the olefin resin composition was determined inthe same manner as in Example I-8 (3). The data are shown in Table I-4.

COMPARATIVE EXAMPLE I-4 Production of Olefin Resin Composition

An olefin resin composition was prepared in the same manner as inExample I-8 (2), for which, however, 100 parts by weight of thelow-stereospecificity polypropylene of Example I-11 (1) was used alone.The relaxation rate of the olefin resin composition was determined inthe same manner as in Example I-8 (3). The data are shown in Table I-4.

COMPARATIVE EXAMPLE I-5 Production of Olefin Resin Composition

An olefin resin composition was prepared in the same manner as inExample I-8 (2), for which, however, 100 parts by weight of thehigh-rubber block polypropylene of Example I-12 (1) was used alone. Therelaxation rate of the olefin resin composition was determined in thesame manner as in Example I-8 (3). The data are shown in Table I-4.

TABLE I-4 Co. Ex. 4 Co. Ex. 5 Resin Composition Example 11 Example 12 A(wt. %) 100 — 100 — B (wt. %) — 100 — 100 Type of Graft Example 10Example 10 — — Polymer (wt. pts.) 3.0 5.0 Relaxation Rate 1.62 1.55 — —(1/R₁) (1/sec) Relaxation Rate — — 1.50 1.45 (1/R₁)₀ (1/sec) Ratio ofRelaxation 1.08 1.07 — — Rate [(1/R₁)/(1/R₁)₀]

-   A: low-stereospecificity polypropylene-   B: high-rubber block polypropylene    II. Second Aspect of the Invention:

In this section, the second aspect of the invention will be simplyreferred to as “the invention”.

The propylene macromonomer [1], the propylene graft copolymer [2] andthe olefin resin composition [3] of the invention are described indetail hereinunder.

[1] Propylene Macromonomer:

The propylene branched macromonomer of the invention is a propylenepolymer satisfying the following (a), (b) and (c):

(a) its weight-average molecular weight (MW) measured through gelpermeation chromatography (GPC) falls between 800 and 500000;

(b) its vinyl content is at least 70 mol % of all the unsaturated groupsin the macromonomer;

(c) its propylene content falls between 50 and 100 mol %.

The propylene macromonomer of the invention (hereinafter this will bereferred to as “the macromonomer”) is a linear propylene polymer havinga low to middle-level molecular weight, in which the terminals of themain chain contain vinyl groups in a specific ratio. Since themacromonomer contains many vinyl groups, it is effective in variouschemical reactions such as typically grafting reaction. In addition,since its molecular weight falls in a broad range of from relatively lowto high molecular weights, it is usable as the material forcompatibilizers for various resins and also as a resin moldabilityimprover.

The weight-average molecular weight (Mw) of the macromonomer of theinvention, measured through GPC, falls between 800 and 500000, butpreferably between 800 and 400000, more preferably between 900 and350000, even more preferably between 1000 and 300000, most preferablybetween 1000 and 250000. Macromonomers having Mw of smaller than 800 areuseless in production of graft copolymers, as their ability to improve aresin compatibility and resin melt tension is not good; but those havingMw of larger than 500000 are unfavorable since the apparent terminalvinyl content thereof is extremely small and the graft copolymerizationefficiency with them is poor.

For GPC for the invention, referred to is the same as that mentioned inthe section of the first aspect of the invention.

In the invention, the vinyl content of the macromonomer falls between 70and 100% of all the unsaturated groups in the macromonomer. Preferably,it falls between 75 and 100%, more preferably between 80 and 100%, mostpreferably between 85 and 100%. If the vinyl content is smaller than70%, the efficiency in grafting reaction with the macromonomer is low,and the residual macromonomer lowers the physical properties of graftpolymers.

The vinyl content relative to all the unsaturated groups in themacromonomer may be measured (1) through ¹H-NMR or (2) through IR. Forthe details of the methods, referred to are the same as those mentionedin the section of the first aspect of the invention. In the invention,employable is any of these methods.

The propylene macromonomer of the invention has a propylene content offrom 50 to 100 mol %, preferably from 55 to 100 mol %, more preferablyfrom 60 to 100 mol %.

If its propylene content is smaller than 50 mol %, the macromonomer isineffective as a compatibilizer for thermoplastic resin blends.

So far as it satisfies the above-mentioned requirements, the propylenemacromonomer [1] is not specifically defined any more. The monomer toconstitute the macromonomer is propylene, or propylene and at least oneselected from ethylene, α-olefins having from 4 to 20 carbon atoms,cyclic olefins and styrenes.

Concretely, the macromonomer is a propylene homopolymer, or a propylenecopolymer of propylene and at least one selected from ethylene,α-olefins having from 4 to 20 carbon atoms, cyclic olefins and styrenes.

The propylene homopolymer includes atactic polypropylene APP, isotacticpolypropylene IPP, and syndiotactic polypropylene SPP. The propylenecopolymer includes IPP-PE, APP-PE and SPP-PE in which PE indicatespolyethylene, and also those for which ethylene is replaced with any ofα-olefins having from 4 to 20 carbon atoms, cyclic olefins and styrenes.

The α-olefins having from 4 to 20 carbon atoms include, for example,α-olefins such as 1-butene, 3-methyl-1-butene, 4-methyl-1-butene,4-phenyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene,1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 6-phenyl-1-hexene,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene, vinylcyclohexane; and halogen-substitutedα-olefins such as hexafluoropropene, tetrafluoroethylene,2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene,trifluoroethylene, 3,4-dichloro-1-butene.

The cyclic olefins includes those of the following general formula(II-1):

-   -   wherein R^(a) to R₁ each represent a hydrogen atom, a        hydrocarbon group having from 1 to 20 carbon atoms, or a        halogen-, oxygen- or nitrogen-containing substituent; m        indicates an integer of 0 or more; R^(i) and R^(j), each        combined with R^(j) and R¹, respectively, may form a ring; and        R^(a) to R¹ may be the same or different.

In the cyclic olefins of formula (II-1), R^(a) to R¹ each represent ahydrogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, ora halogen-, oxygen- or nitrogen-containing substituent, as so mentionedhereinabove.

Concretely, the hydrocarbon group having from 1 to 20 carbon atomsincludes, for example, an alkyl group having from 1 to 20 carbon atomssuch as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyland hexyl groups; an aryl, alkylaryl or arylalkyl group having from 6 to20 carbon atoms such as phenyl, tolyl and benzyl groups; an alkylidenegroup having from 1 to 20 carbon atoms such as methylidene, ethylideneand propylidene groups; and an alkenyl group having from 2 to 20 carbonatoms such as vinyl and allyl groups. However, R^(a), R^(b), R^(e) andR^(f) must not be an alkylene group. In case where any of R^(c), R^(d),R^(g) to R^(l) is an alkylidene group, the carbon atom to which it isbonded does not have any other substituent.

Concretely, the halogen-containing substituent includes, for example, ahalogen atom such as fluorine, chlorine, bromine and iodine atoms; and ahalogen-substituted alkyl group having from 1 to 20 carbon atoms such aschloromethyl, bromomethyl and chloroethyl groups.

The oxygen-containing substituent includes, for example, an alkoxy grouphaving from 1 to 20 carbon atoms such as methoxy, ethoxy, propoxy andphenoxy groups; and an alkoxycarbonyl group having from 1 to 20 carbonatoms such as methoxycarbonyl and ethoxycarbonyl groups.

The nitrogen-containing substituent includes, for example, an alkylaminogroup having from 1 to 20 carbon atoms such as dimethylamino anddiethylamino groups, and a cyano group.

Examples of the cyclic olefins of formula (II-1) are norbornene,5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene,5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene,5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene,5-ethylidenenorbornene, 5-vinylnorbornene,1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octhydronaphthalene,2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,1,2-dihydrocyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene,5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene,5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxynorborneneanhydrate, 5-dimethylaminonorbornene, and 5-cyanonorbornene.

The styrenes for use herein are not specifically defined, but preferredare styrene, alkylstyrenes, and divinylbenzene. More preferred arestyrene, α-methylstyrene, p-methylstyrene and divinylbenzene.

The styrenes include, for example, styrene; alkylstyrenes such asp-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene,p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene,o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene,m-ethylstyrene, m-isopropylstyrene, m-butylstyrene, mesitylstyrene,2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene;alkoxystyrenes such as p-methoxystyrene, o-methoxystyrene,m-methoxystyrene; and halogenostyrenes such as p-chlorostyrene,m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene,o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene,o-methyl-p-fluorostyrene. Further mentioned are trimethylsilylstyrene,vinylbenzoates, and divinylbenzene.

Of those, ethylene is preferred for the comonomer. In the invention, oneor more of the above-mentioned olefins may be used either singly or ascombined in any desired manner.

The macromonomer of the invention can be produced by polymerizingpropylene, or propylene and at least one comonomer selected fromethylene, α-olefins having from 4 to 20 carbon atoms, cyclic olefins andstyrenes, in the presence of a catalyst comprising (A) a transitionmetal compound of Group 4 of the Periodic Table of the following generalformula (II-2), (B) at least one selected from a compound groupconsisting of (B-1) aluminoxanes and (B-2) compounds capable of formingionic complexes from the transition metal compound or its derivatives,and optionally (C) an organoaluminium compound.(R¹ _(5-m)H_(m)C₅)(R² _(5-n)H_(n)C₅)M¹X¹ ₂  (II-2)wherein M¹ represents titanium, zirconium or hafnium; R¹ and R² eachrepresent a hydrocarbon group having from 1 to 20 carbon atoms, andthese may be the same or different; (R¹ _(5-m)H_(m)C₅) and (R²_(5-n)H_(n)C₅) each represent a hydrocarbon-substituted cyclopentadienylgroup, and these may be the same or different; X¹ represents a hydrogenatom, a halogen atom, or a hydrocarbon group having from 1 to 20 carbonatoms, and two X¹'s may be the same or different; m and n eachindependently represent 0, 1 or 2, but these must not be m=n=0 at thesame time.

In formula (II-2), the hydrocarbon group having from 1 to 20 carbonatoms for R¹, R² and X¹ is not specifically defined. Preferably, forexample, it is an alkyl, aryl, arylalkyl or alkylaryl group having from1 to 20 carbon atoms. The alkyl group having from 1 to 20 carbon atomsincludes, for example, methyl, ethyl, propyl, isopropyl, butyl,isobutyl, t-butyl, amyl, hexyl, heptyl, octyl, nonyl, capryl, undecyl,lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl,nonadecyl and eicosyl groups. The aryl and arylalkyl groups having from1 to 20 carbon atoms include, for example, phenyl, benzyl and phenethylgroups. The alkylaryl group having from 1 to 20 carbon atoms includes,for example, p-tolyl and p-n-butylphenyl groups.

In compounds of formula (II-2), for example, (R¹ _(5-m)H_(m)C₅) and (R²_(5-n)H_(n)C₅) are the same. Concretely, they includebis(1,2-dimethyl-3,5-diethylcyclopentadienyl)zirconium dichloride,bis(1,2-dimethyl-3,5-di-n-butylcyclopentadienyl)zirconium dichloride,bis(1-n-butyl-2,3,4-trimethylcyclopentadienyl)zirconium dichloride,bis(1,2,4-trimethylcyclopentadienyl)zirconium dichloride,bis(1,2-dimethyl-4-ethylcyclopentadienyl)zirconium dichloride,bis(1-methyl-2,4-diethylcyclopentadienyl)zirconium dichloride,bis(1,2,4-triethylcyclopentadienyl)zirconium dichloride,bis(1,2-diethyl-4-methylcyclopentadienyl)zirconium dichloride, andbis(1,2-dimethyl-4-isopropylcyclopentadienyl)zirconium dichloride.

Examples of the compounds in which (R¹ _(5-m)H_(m)C₅) and (R²_(5-n)H_(n)C₅) differ from each other are(pentamethylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride,(pentamethylcyclopentadienyl)(1,2,4-trimethylcyclopentadienyl)zirconiumdichloride,(pentamethylcyclopentadienyl)(1,2-dimethyl-3,5-diethylcyclopentadienyl)zirconiumdichloride,(pentamethylcyclopentadienyl)(1,2-dimethyl-3,5-di-n-butylcyclopentadienyl)zirconiumdichloride,(pentamethylcyclopetandienyl)(1-n-butyl-2,3,4-trimethylcyclopentadienyl)zirconiumdichloride,(pentamethylcyclopentadienyl)(1-methyl-2,4-diethylcyclopentadienyl)zirconiumdichloride,(pentamethylcyclopentadienyl)(1,2-dimethyl-4-ethylcyclopentadienyl)zirconiumdichloride,(pentamethylcyclopentadienyl)(1,2,4-triethylcyclopentadienyl)zirconiumdichloride,(pentamethylcyclopentadienyl)(1,2-diethyl-4-methylcyclopentadienyl)zirconiumdichloride,(pentamethylcyclopentadienyl)(1,2-dimethyl-4-isopropylcyclopentadienyl)zirconiumdichloride,(tetramethylcyclopentadienyl)(1,2,4-trimethylcyclopentadienyl)zirconiumdichloride,(tetraethylcyclopentadienyl)(1,2,4-trimethylcyclopentadienyl)zirconiumdichloride, and(1,2-dimethyl-3,5-diethylcyclopentadienyl)(1,2,4-trimethylcyclopentadienyl)zirconiumdichloride.

For the component (A), two or more different types of the compounds maybe combined.

The aluminoxanes for the component (B-1) include linear aluminoxanes ofa general formula (II-3):

wherein R¹ represents a hydrocarbon group, such as an alkyl, alkenyl,aryl or arylalkyl group having from 1 to 20, preferably from 1 to 12carbon atoms, or represents a halogen atom; w indicates a mean degree ofpolymerization, and is an integer generally falling between 2 and 50,preferably between 2 and 40; and R³'s may be the same or different, andcyclic aluminoxanes of a general formula (II-4):

wherein R³ and w have the same meanings as those in formula (II-3).

For producing the aluminoxanes mentioned above, for example, employableis a method of contacting alkylaluminiums with a condensation agent suchas water, for which, however, the means are not specifically defined.The reaction in the method may be effected in any known manner. Forexample, <1> an organoaluminium compound is dissolved in an organicsolvent, and this is contacted with water; <2> an organoaluminiumcompound is added to the polymerization system, and water is addedthereto later; <3> crystal water existing in metal salts and the like,or water adsorbed by inorganic or organic matters is applied to andreacted with an organoaluminium compound; <4> a tetraalkyldialuminoxaneis reacted with a trialkylaluminium, and then with water.

The aluminoxanes may be soluble or insoluble in hydrocarbon solvents.Preferably, however, they are soluble in hydrocarbon solvents, and havea residual organoaluminium compound content of at most 10% by weightmeasured through ¹H-NMR. More preferably, they have a residualorganoaluminium compound content of from 3 to 5% by weight or smaller,even more preferably from 2 to 4% by weight or smaller. The aluminoxanesof the type are preferred, as the percentage of the aluminoxane to beheld on a carrier (carrier-held percentage) increases. Another advantageis that, since they are soluble in hydrocarbon solvents, those not heldon a carrier can be recycled. In addition, the properties of thealuminoxanes of the type are stable, and therefore, they do not requireany additional treatment before use. Moreover, the polyolefins producedthrough polymerization in the presence of such aluminoxanes are good inpoint of their mean particle size and particle size distribution(morphology as a generic term for these). These are other advantages ofthe aluminoxanes of the type. If, however, the residual organoaluminiumcompound content thereof is larger than 10% by weight, the aluminoxaneswill lower the polymerization activity of the catalyst comprising it.

To obtain the preferred aluminoxanes, for example, employable is aso-called dry-up method that comprises dissolving an ordinaryaluminoxane in a solvent, followed by drying up the resultingaluminoxane solution under heat under reduced pressure to remove thesolvent. In the dry-up method, it is preferable that the aluminoxanesolution is heated under reduced pressure at a temperature not higherthan 80° C., more preferably not higher than 60° C. for removing thesolvent.

For removing the matters insoluble in hydrocarbon solvents fromaluminoxanes, for example, the insoluble matters are spontaneouslyprecipitated in an aluminoxane solution in a hydrocarbon solvent andthen removed from the solution through decantation. Alternatively, theinsoluble matters may also be removed through centrifugation or thelike. With that, the solubilized component thus recovered is filteredthrough a G5 glass filter or the like in a nitrogen atmosphere. Themethod is preferable as it ensures complete removal of the insolublematters. The aluminoxanes thus prepared will often gel when stored forlong. Therefore, it is desirable that they are used in the inventionwithin 48 hours after their preparation. More preferably, they are usedimmediately after their preparation. The proportion of the aluminoxaneto the hydrocarbon solvent in which it is processed is not specificallydefined, but it is desirable that the aluminoxane concentration in thehydrocarbon solvent falls between 0.5 and 10 mols, in terms of thealuminium atom, in one liter of the hydrocarbon solvent.

The hydrocarbon solvent includes, for example, aromatic hydrocarbonssuch as benzene, toluene, xylene, cumene, cymene; aliphatic hydrocarbonssuch as pentane, hexane, heptane, octane, decane, dodecane, hexadecane,octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane,cyclooctane, methylcyclopentane; petroleum fractions such as naphtha,kerosene, light gas oil. One or more different types of suchaluminoxanes may be used either singly or as combined.

For the component (B-2), usable are any ionic compounds capable of beingconverted into cations through reaction with the above-mentionedtransition metal compound. Especially preferred for use herein arecompounds of the following general formulae (II-5) and (II-6), as beingable to efficiently form polymerization-active points.([L¹-R⁴]^(h+))_(a)([Z]⁻)_(b)  (II-5)([L²]^(h+))_(a)([Z]⁻)_(b)  (II-6)In these, L² represents M², R⁵R⁶M³, R⁷ ₃C or R⁸M³.

In formulae (II-5) and (II-6), L¹ represents a Lewis base; [Z]⁻represents a non-coordinating anion [Z¹]⁻ or [Z²]⁻; [Z¹]⁻ represents ananion of a plurality of groups bonded to an element, [M⁴G¹G² . . .G^(f)]⁻¹; M⁴ represents an element of Groups 5 to 15 of the PeriodicTable, preferably an element of Groups 13 to 15 of the Periodic Table;G¹ to G^(f) each represents a hydrogen atom, a halogen atom, an alkylgroup having from 1 to 20 carbon atoms, a dialkylamino group having from2 to 40 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms,an aryl group having from 6 to 20 carbon atoms, an aryloxy group havingfrom 6 to 20 carbon atoms, an alkylaryl group having from 7 to 40 carbonatoms, an arylalkyl group having from 7 to 40 carbon atoms, ahalogen-substituted hydrocarbon group having from 1 to 20 carbon atoms,an acyloxy group having from 1 to 20 carbon atoms, an organometalloidgroup, or a hetero atom-containing hydrocarbon group having from 2 to 20carbon atoms, and at least two of G¹ to G^(f) may form a ring; f is aninteger, indicating [(atomic valency of the center metal M⁴)+1]; [Z²]⁻represents a conjugated base of a single Brøonsted acid of which thelogarithm of the reciprocal of the acid dissociation constant (pK_(a))is at most −10, or of a combination of such a Brønsted acid and a Lewisacid, or represents a conjugated base of an ordinary ultra-strong acid,and optionally, this may be coordinated with a Lewis base; R⁴ representsa hydrogen atom, an alkyl group having from 1 to 20 carbon atoms, anaryl, alkylaryl or arylalkyl group having from 6 to 20 carbon atoms; R⁵and R⁶ each represent a cyclopentadienyl group, a substitutedcyclopentadienyl group, an indenyl group, or a fluorenyl group; R⁷represents an alkyl, aryl, alkylaryl or arylalkyl group having from 1 to20 carbon; R⁸ represents a macrocyclic ligand such astetraphenylporphyrin or phthalocyanine; h is an integer of from 1 to 3,indicating the ionic valency of [L¹—R⁴] or [L²]; a is an integer of atleast 1; b=(h×a); M² represents an element of Groups 1 to 3, 11 to 13and 17 of the Periodic Table; and M³ represents an element of Groups 7to 12 of the Periodic Table.

Examples of L¹ are amines such as ammonia, methylamine, aniline,dimethylamine, diethylamine, N-methylaniline, diphenylamine,N,N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine,methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline,p-nitro-N,N-dimethylaniline; phosphines such as triethylphosphine,triphenylphosphine, diphenylphosphine; thioethers such astetrahydrothiophene; esters such as ethyl benzo ate; nitriles such asacetonitrile, benzonitrile.

Examples of R⁴ are a hydrogen atom, a methyl group, an ethyl group, abenzyl group, a trityl group. Examples of R⁵ and R⁶ are acyclopentadienyl group, a methylcyclopentadienyl group, anethylcyclopentadienyl group, a pentamethylcyclopentadienyl group.Examples of R⁷ are a phenyl group, a p-tolyl group, a p-methoxyphenylgroup. Examples of R⁸ are tetraphenylporphine, phthalocyanine, allyl,methallyl. Examples of M² are Li, Na, K, Ag, Cu, Br, I, I₃. Examples ofM³ are Mn, Fe, Co, Ni, Zn.

In [Z¹]⁻ indicating [M⁵G¹G² . . . G^(f)]⁻, M⁵ includes B, Al, Si, P, As,Sb, but is preferably B or Al. Examples of the dialkylamino group forG¹, G² to G^(f) are a dimethylamino group, a diethylamino group; thoseof the alkoxy group and the aryloxy group are a methoxy group, an ethoxygroup, an n-butoxy group, a phenoxy group; those of the hydrocarbongroup are a methyl group, an ethyl group, an n-propyl group, anisopropyl group, an n-butyl group, an isobutyl group, an n-octyl group,an n-eicosyl group, a phenyl group, a p-tolyl group, a benzyl group, a4-t-butylphenyl group, a 3,5-dimethylphenyl group; those of the halogenatom are fluorine, chlorine, bromine and iodine atoms; those of thehetero atom-containing hydrocarbon group are a p-fluorophenyl group, a3,5-difluorophenyl group, a pentachlorophenyl group, a3,4,5-trifluorophenyl group, a pentafluorophenyl group, a3,5-bis(trifluoromethyl)phenyl group, a bis(trimethylsilyl)methyl group;those of the organometalloid group are a pentamethylantimonyl group, atrimethylsilyl group, a trimethylgermyl group, a diphenylarsenyl group,a dicyclohexylantimonyl group, a diphenylboryl group.

Examples of the non-coordinating anion, [Z²]⁻ that indicates aconjugated base of a single Brønsted acid having pKa of at most −10, orof a combination of such a Brønsted acid and a Lewis acid are atrifluoromethanesulfonate anion (CF₃SO₃)⁻, abis(trifluoromethanesulfonyl)methyl anion, abis(trifluoromethanesulfonyl)benzyl anion, a bis(trifluoromethanesulfonyl)amido anion, a perchlorate anion (ClO₄)⁻, atrifluoroacetate anion (Cf₃CO₂)⁻, a hexafluoroantimonyl anion (SbF₆)⁻, afluorosulfonate anion (FSO₃)⁻, a chlorosulfonate anion (ClSO₃)⁻, afluorosulfonate/pentafluoroantimonyl anion (FSO₃/SbF₅)⁻, afluorosulfonate/pentafluoroarsenyl anion (FSO₃/AsF₅)⁻, atrifluoromethanesulfonate/pentafluoroantimonyl anion (CF₃SO₃SbF₅)⁻.

Examples of the compounds for the component (B-2) are triethylammoniumtetraphenylborate, tri-n-butylammonium tetraphenylborate,trimethylammonium tetraphenylborate, tetraethylammoniumtetraphenylborate, methyl(tri-n-butyl)ammonium tetraphenylborate,benzyl(tri-n-butyl)ammonium tetraphenylborate, dimethyldiphenylammoniumtetraphenylborate, triphenyl(methyl)ammonium tetraphenylborate,trimethylanilinium tetraphenylborate, methylpyridiniumtetraphenylborate, benzylpyridinium tetraphenylborate,methyl(2-cyanopyridinium) tetraphenylborate, triethylammoniumtetrakis(pentafluorophenyl)borate, tri-n-butylammoniumtetrakis(pentafluorophenyl)borate, triphenylammoniumtetrakis(pentafluorophenyl)borate, tetra-n-butylammoniumtetrakis(pentafluorophenyl)borate, tetraethylammoniumtetrakis(pentafluorophenyl)borate, benzyl(tri-n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, methyldiphenylammoniumtetrakis(pentafluorophenyl)borate, triphenyl(methyl) ammonium tetrakis(pentafluorophenyl)borate, methylaniliniumtetrakis(pentafluorophenyl)borate, dimethylaniliniumtetrakis(pentafluorophenyl)borate, methylaniliniumtetrakis(pentafluorophenyl)borate, methylpyridiniumtetrakis(pentafluorophenyl)borate, methylpyridiniumtetrakis(pentafluorophenyl)borate, methyl(2-cyanopyridinium)tetrakis(pentafluorophenyl)borate, benzyl(2-cyanopyridinium)tetrakis(pentafluorophenyl)borate, methyl(4-cyanopyridinium)tetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, dimethylaniliniumtetrakis[bis(3,5-ditrifluoromethyl)phenyl]borate, ferroceniumtetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate,tetraphenylporphyrylmanganese tetraphenylborate, ferroceniumtetrakis(pentafluorophenyl)borate, (1,1′-dimethylferrocenium)tetrakis(pentafluorophenyl)borate, decamethylferroceniumtetrakis(pentafluorophenyl)borate, silvertetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, sodiumtetrakis(pentafluorophenyl)borate, tetraphenylporphyrylmanganesetetrakis(pentafluorophenyl)borate, silver tetrafluoroborate, silverhexafluorophosphate, silver hexafluoroarsenate, silver perchlorate,silver trifluoroacetate, and silver trifluoromethanesulfonate. For thecomponent (B-2), preferred are the boron compounds mentioned above.

For the component (B-2), one or more different types of ionic compoundscapable of being converted into cations through reaction with thetransition metal compound of the component (A) may be used, eithersingly or as combined.

In the olefin polymerization catalyst for use in the invention, thecomponent (B) may be the component (B-1) or (B-2) alone, or acombination of the components (B-1) and (B-2).

The catalyst for producing the macromonomer of the invention mayconsists, as the essential ingredients, the component (A) and thecomponent (B) mentioned above, or may consists, as the essentialingredients, the component (A), the component (B) and theorganoaluminium compound (C). The organoaluminium compound for thecomponent (C) includes those of a general formula (II-7):R⁹ _(v)AlQ_(3-v)  (II-7)wherein R9 represents an alkyl group having from 1 to 10 carbon atoms; Qrepresents a hydrogen atom, an alkoxy group having from 1 to 20 carbonatoms, an aryl group having from 6 to 20 carbon atoms, or a halogenatom; and v is an integer of from 1 to 3.

Examples of the compounds of formula (II-7) are trimethylaluminium,triethylaluminium, triisopropylaluminium, triisobutylaluminium,dimethylaluminium chloride, diethylaluminium chloride, methylaluminiumdichloride, ethylaluminium dichloride, dimethylaluminium fluoride,diisobutylaluminium hydride, diethylaluminium hydride, andethylaluminium sesquichloride. One or more different types of theorganoaluminium compounds may be used herein either singly or ascombined.

The proportion of the catalyst components (A) and (B) of thepolymerization catalyst for use in the invention is described. In casewhere the compound (B-1) is used for the catalyst component (B), themolar ratio of the two components preferably falls between 1/1 and1/10⁶, more preferably between 1/10 and 1/10³. If the ratio overstepsthe range, the catalyst cost per the unit weight of the polymer producedincreases and is therefore impracticable. In case where the compound(B-2) is used, the molar ratio preferably falls between 1/0.1 and 1/100,more preferably between 1/0.5 and 1/10, even more preferably between1/0.8 and 1/5. If the ratio oversteps the range, the catalyst cost perthe unit weight of the polymer produced increases and is thereforeimpracticable.

The molar ratio of the catalyst component (A) to the optional catalystcomponent (C) preferably falls between 1/1 and 1/1000, more preferablybetween 1/10 and 1/700, even more preferably between 1/20 and 1/500. Thecatalyst component (C), if any, improves the polymerization activity perthe transition metal of the catalyst. However, if too much, oversteppingthe range as above, it is undesirable since the excess organoaluminiumcompound comes to nothing and will remain in the polymer produced; butif too small, it is also undesirable since the catalyst activity is low.

In the invention, at least one catalyst component may be held on asuitable carrier. The type of the carrier is not specifically defined.For the carrier, for example, usable are inorganic oxides, and alsoother inorganic carriers and organic carriers. For morphology control ofthe polymers produced, preferred are inorganic oxides and otherinorganic carriers. Concretely, the inorganic oxide carriers includeSiO₂, Al₂O₃, MgO, ZrO₂, TiO₂, Fe₂O₃, B₂O₃, CaO, ZnO, BaO, Tho₂, andtheir mixtures such as silica-alumina, zeolite, ferrite and glassfibers. Of those, especially preferred are SiO₂ and Al₂O₃. The inorganicoxide carriers may contain minor carbonates, nitrates, sulfates, etc.Other examples of the carriers than those mentioned above are magnesiumcompounds of a general formula MgR¹⁰ _(x)X² _(y) such as typically MgCl₂and Mg(OC₂H₅)₂, and their complexes. In the formula, R¹⁰ represents analkyl group having from 1 to 20 carbon atoms, an alkoxy group havingfrom 1 to 20 carbon atoms, or an aryl group having from 6 to 20 carbonatoms; X² represents a halogen atom, or an alkyl group having from 1 to20 carbon atoms; x falls between 0 and 2; y falls between 0 and 2; andx+y=2. R¹⁰'s as well as X²'s, if any, may be the same or different. Theorganic carriers usable herein include, for example, polymers such aspolystyrene, styrene-divinylbenzene copolymer, polyethylene,polypropylene, substituted polystyrene, polyarylate; and starch andcarbon. For the carrier for use in the invention, preferred are MgCl₂,MgCl(OC₂H₅), Mg(OC₂H₅)₂, SiO₂ and Al₂O₃. The properties of the carriersvary, depending on their type and the method for producing them. Ingeneral, their mean particle size falls between 1 and 300 μm, preferablybetween 10 and 200 μm, more preferably between 20 and 100 μm. If thecarriers are too small, fine powder in the polymers produced willincrease; but if too large, coarse particles in the polymers producedwill increase and they lower the bulk density of the polymers and cloghoppers. The specific surface area of the carriers may fall generallybetween 1 and 1000 m²/g, preferably between 50 and 500 m²/g; and thepore volume thereof may fall generally between 0.1 and 5 cm³/g,preferably between 0.3 and 3 cm³/g. If any of the specific surface areaand the pore volume of the carrier used oversteps the range, thecatalyst activity will lower. The specific surface area and the porevolume of the carriers may be calculated from the volume of the nitrogengas adsorbed by the carriers, for example, according to the BET method(see J. Am. Chem. Soc., Vol. 60, p. 309, 1983). Preferably, the carriersare calcined generally at a temperature falling between 100 and 1000°C., preferably between 130 and 800° C. before use.

In case where at least one catalyst component is held on carriers, it isdesirable that at least one of the catalyst components (A) and (B),preferably both of them are held on the carrier from the viewpoint ofthe morphology control of polymers and of the process applicability ofthe catalyst, for example, to vapor-phase polymerization.

The method of making at least one of the components (A) and (B) held oncarriers is not specifically defined. For example, <1> at least one ofthe components (A) and (B) is mixed with a carrier; <2> a carrier isprocessed with an organoaluminium compound or a halogen-containingsilicon compound, and then it is mixed with at least one of thecomponents (A) and (B) in an inert solvent; <3> a carrier is, along withthe component (A) or (B) or with the two, reacted with anorganoaluminium compound or a halogen-containing silicon compound; <4>the component (A) or (B) is first held on a carrier, and then thecomponents (A) and (B) are mixed; <5> a contact reaction product of thecomponents (A) and (B) is mixed with a carrier; or <6> the components(A) and (B) are contacted in the presence of a carrier. In the methods<4>, <5> and <6>, an organoaluminium compound for the component (C) maybe added to the system.

In the invention, the blend ratio of the component (B-1) and the carrierpreferably falls between 1/0.5 and 1/1000, more preferably between 1/1and 1/50 by weight. The blend ratio of the component (B-2) and thecarrier preferably falls between 1/5 and 1/10000, more preferablybetween 1/10 and 1/500 by weight. In case where two or more differenttypes of compounds are combined and used for the catalyst component (B),it is desirable that the blend ratio of each compound for the component(B) and the carrier falls within the range as above. The blend ratio ofthe component (A) and the carrier preferably falls between 1/5 and1/10000, more preferably between 1/10 and 1/500 by weight.

The blend ratio of the component (B) (component (B-1), component (B-2))and the carrier, or the blend ratio of the component (A) and the carrieroversteps the range as above, the catalyst activity will lower. The meanparticle size of the polymerization catalyst prepared in the manner asabove for use in the invention may fall generally between 2 and 200 μm,preferably between 10 and 150 μm, more preferably between 20 and 100 μm;and the specific surface area thereof may fall generally between 20 and1000 m²/g, preferably between 50 and 500 m²/g. If the mean particle sizeis smaller than 2 μm, fine powder in the polymers produced willincrease; but if larger than 200 μm, coarse particles in the polymerswill increase. If the specific surface area is smaller than 20 m²/g, thecatalyst activity will lower; but if larger than 1000 m²/g, the bulkdensity of the polymers produced will lower. In the polymerizationcatalyst, the amount of the transition metal preferably falls between0.05 and 10 g, more preferably between 0.1 and 2 g, per 100 g of thecarrier therein. If the amount of the transition metal oversteps therange, the catalyst activity will lower. Using the catalyst held on acarrier, the olefin polymers produced have an increased bulk density anda desired particle size distribution and are therefore favorable forindustrial applications.

The treatment for contacting the component (A), the component (C) andoptionally the component (C) and/or carrier with each other may beeffected in an inert gas such as nitrogen, or in a hydrocarbon solventsuch as pentane, hexane, heptane, toluene or cyclohexane. Thetemperature for the contact treatment may fall between −30° C. and theboiling point of the solvent used, preferably between −10° C. and 100°C.; the time for it may fall generally between 30 seconds and 10 hours.After the contact treatment, the solid catalyst component may be or maynot be washed. The catalyst thus prepared may be used for polymerizationafter it is once subjected to distillation for solvent removal toseparate the solid catalyst, or may be directly used with no suchtreatment.

In the invention, the treatment for making at least one of thecomponents (A) and (B) held on a carrier may be effected in thepolymerization system to form the catalyst in situ. For example, atleast one of the components (A) and (B) and a carrier, and optionally anorganoaluminium compound for the component (C) are put in a reactor, inwhich an olefin is prepolymerized to form the catalyst. The olefin to beused for the prepolymerization may be any of ethylene and α-olefinshaving from 3 to 20 carbon atoms, such as propylene, 1-butene,1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene,and 1-tetradecene. Of those, especially preferred are ethylene,propylene, and their combinations with α-olefins for ethylene-propylenepolymerization. For the inert hydrocarbon solvent for theprepolymerization, referred to are the same as those mentionedhereinabove for the preparation of solid catalyst components. The amountof the components to be processed through such prepolymerization mayfall generally between 10⁻⁶ and 2×10² mols/liter (solvent), in terms ofthe transition metal therein, preferably between 5×10⁻⁵ and 10⁻²mols/liter (solvent). In one gram of the carrier, the atomic ratio ofthe aluminium in the organoaluminium compound such as methylaluminoxane(MAO), to the transition metal, (Al/transition metal), generally fallsbetween 10 and 5000, preferably between 20 and 1000. The atomic ratio ofthe aluminium atom in the optional organoaluminium compound to thealuminium atom in MAO generally falls between 0.02 and 3, preferablybetween 0.05 and 1.5. The prepolymerization temperature may fall between−20 and 60° C., preferably between 0 and 50° C. The prepolymerizationtime may fall between 0.5 and 100 hours, preferably between 1 and 50hours or so. In the invention, the catalyst to be used is preferablyprepared through olefin prepolymerization.

Regarding the polymerization condition in producing the macromonomer ofthe invention, the ratio of the monomer concentration to theconcentration of the linear macromonomer produced in the reaction systemmust be large in order to control the molecular weight of themacromonomer and to make the macromonomer have a linear structure. Inthat condition, the linear macromonomer produced is prevented from beingfurther copolymerized with the monomer in the reaction system to formbranches, and therefore the efficiency in producing the intended linearmacromonomer is increased. For example, it is desirable that the monomerconcentration in the reaction system is increased, or that is, thereaction pressure is increased or the reaction temperature is lowered.This is for preventing the formation of branched macromonomers, and, inaddition, for increasing the molecular weight of the intended linearmacromonomer produced, whereby undesirable oligomers such as dimers andtrimers, to which the invention is not directed, are prevented frombeing formed. Concretely, the following polymerization condition 1 or 2is employed.

Polymerization Condition 1:

The polymerization temperature falls between −50° C. and lower than 20°C., preferably between −50° C. and 18° C., more preferably between −40°C. and 16° C., even more preferably between −35° C. and 15° C. Withinthe polymerization temperature range, the polymerization pressure fallsgenerally between 0.001 and 5 MPa (gauge), preferably between 0.005 and5 MPa (gauge), more preferably between 0.005 and 4 MPa (gauge), evenmore preferably between 0.01 and 3.5 MPa (gauge).

Polymerization Condition 2:

The polymerization temperature falls between 40° C. and 100° C.,preferably between 40° C. and 90° C., more preferably between 45° C. and90° C., even more preferably between 45° C. and 80° C. Within thepolymerization temperature range, the polymerization pressure fallsgenerally between 1.5 and 15 MPa (gauge), preferably between 2 and 15MPa (gauge), more preferably between 2.4 and 15 MPa (gauge).

The polymerization may be effected in any mode of solutionpolymerization, bulk polymerization or vapor-phase polymerization. Thesolvent to be used in the polymerization includes, for example, aromatichydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbonssuch as hexane, heptane; and alicyclic hydrocarbons such s cyclopentane,cyclohexane.

[2]Propylene Graft Copolymer:

The propylene graft copolymer of the invention is a polymer obtained bycopolymerizing the above-mentioned propylene macromonomer [1] with atleast one comonomer selected from ethylene, propylene, α-olefins havingfrom 4 to 20 carbon atoms, cyclic olefins and styrenes, in the presenceof a metallocene catalyst or a Ziegler-Natta catalyst, preferably in thepresence of a metallocene catalyst.

The propylene graft copolymer of the invention may have or may not haveterminal vinyl groups, but preferably has no terminal vinyl groups. Itmay be any of random copolymers or block copolymers. Regarding itsstereospecificity, the copolymer may be any of atactic, isotactic orsyndiotactic copolymers.

Preferably, the propylene graft copolymer of the invention contains from0.01 to 40% by weight, more preferably from 0.02 to 40% by weight, evenmore preferably from 0.02 to 35% by weight of the above-mentionedpropylene macromonomer.

If its propylene macromonomer content is smaller than 0.01% by weight,the copolymer is ineffective for improving the workability of resincompositions containing it; but if larger than 40% by weight, the meltflowability of the resin compositions lowers.

Preferably, the propylene graft copolymer of the invention satisfies thefollowing (1) and/or (2):

(1) its intrinsic viscosity [η] measured in a solvent decalin at 135° C.falls between 0.3 and 15 dl/g;

(2) the ratio of the weight-average molecular weight (Mw) to thenumber-average molecular weight (Mn) thereof measured through GPC,Mw/Mn, falls between 1.5 and 4.5.

If the copolymer does not satisfy the above (1), or that is, if its [η]is smaller than 0.3, its mechanical strength is not so good; but iflarger than 15, its workability is often poor. If it does not satisfythe above (2), propylene graft copolymers having Mw/Mn of smaller than1.5 are impossible to produce in the current arts. On the other hand,those having the ratio of larger than 4.5 contain a large amount oflow-molecular weight matters, and, in addition, sticky matters increasein them. The mechanical properties, the optical properties(transparency) and other properties such as heat-sealability of thecopolymers are not good.

More preferably, the copolymer satisfies the following (3) and/or (4):

(3) its intrinsic viscosity [η] measured in a solvent decalin at 135° C.falls between 0.5 and 14 dl/g;

(4) the ratio of the weight-average molecular weight (Mw) to thenumber-average molecular weight (Mn) thereof measured through GPC,Mw/Mn, falls between 1.5 and 4.0.

Even more preferably, it satisfies the following (5) and/or (6):

(5) its intrinsic viscosity [η] measured in a solvent decalin at 135° C.falls between 0.6 and 13 dl/g;

(6) the ratio of the weight-average molecular weight (Mw) to thenumber-average molecular weight (Mn) thereof measured through GPC,Mw/Mn, falls between 1.5 and 3.8.

Most preferably, it satisfies the following (7) and/or (8):

(7) its intrinsic viscosity [η] measured in a solvent decalin at 135° C.falls between 0.7 and 12 dl/g;

(8) the ratio of the weight-average molecular weight (Mw) to thenumber-average molecular weight (Mn) thereof measured through GPC,Mw/Mn, falls between 1.5 and 3.0.

One example of the metallocene catalysts usable in producing thepropylene graft copolymer of the invention comprises, as the essentialingredients, (A) a metal or lanthanoid-series transition metal compoundof Groups 3 to 10 of the Periodic Table, and (B) at least one selectedfrom a compound group consisting of (B-1) aluminoxanes and (B-2)compounds capable of forming ionic complexes from the transition metalcompound or its derivatives. Concretely, for example, the metallocenecatalysts described in the applicant's own Japanese Patent Laid-Open No.2942/1995 are usable herein. More concretely, the component (A) includes(i) a monocyclopentadienyl-type metallocene catalyst in which the ligandhas at least one cyclopentadienyl group; (ii) a biscyclopentadienyl-typemetallocene catalyst in which the ligand has at least twocyclopentadienyl groups, (iii) a crosslinked biscyclopentadienyl-typemetallocene catalyst in which the ligand has at least twocyclopentadienyl groups crosslinked, (iv) a restrained geometricmetallocene catalyst, and (v) a double-crosslinked metallocene catalyst.

The above (i) includes transition metal compounds of the followinggeneral formula, and their derivatives.C_(p)M⁶R¹¹ _(a)R¹² _(b)R¹³ _(α)  (II-8).

The above (ii) includes transition metal compounds of the followinggeneral formula, and their derivatives.C_(p2)M⁶R¹¹ _(a)R¹² _(b)  (II-9).

The above (iii) includes transition metal compounds of the followinggeneral formula, and their derivatives.(C_(p)—A_(e)—C_(p))M⁶R¹¹ _(a)R¹² _(b)  (II-10).

In formulae (II-9) to (II-10), M represents a transition metal such astitanium, zirconium, hafnium, vanadium, niobium, chromium; C_(p)represents a cyclic unsaturated hydrocarbon group or a linearunsaturated hydrocarbon group, such as a cyclopentadienyl group, asubstituted cyclopentadienyl group, an indenyl group, a substitutedindenyl group, a tetrahydroindenyl group, a substitutedtetrahydroindenyl group, a fluorenyl group, or a substituted fluorenylgroup; R¹¹, R¹² and R¹³ each independently represent a o-bonding ligand,a chelating ligand, a Lewis base-derived ligand. Concretely, theσ-bonding ligand includes, for example, a hydrogen atom, an oxygen atom,a halogen atom, an alkyl group having from 1 to 20 carbon atoms, analkoxy group having from 1 to 20 carbon atoms, an aryl, alkylaryl orarylalkyl group having from 6 to 20 carbon atoms, an acyloxy grouphaving from 1 to 20 carbon atoms, an allyl group, a substituted allylgroup, a silicon-containing substituent; the chelating ligand includes,for example, an acetylacetonato group and a substituted acetylacetonatogroup. A indicates a covalent-bonding crosslinking group. a, b and ceach independently represent an integer of from 0 to 3; and e representsan integer of from 0 to 6. At least two of R¹¹, R¹² and R¹³ may bebonded to each other to form a ring. When C_(p) has a substituent, thesubstituent is preferably an alkyl group having from 1 to 20 carbonatoms. In formulae (II-9) and (II-10), two C_(p)'s may be the same ordifferent.

The substituted cyclopentadienyl group in formulae (II-8) to (II-10)includes, for example, methylcyclopentadienyl, ethylcyclopentadienyl,isopropylcyclopentadienyl, 1,2-dimethylcyclopentadienyl,tetramethylcyclopentadienyl, 1,3-dimethylcyclopentadienyl,1,2,3-trimethylcyclopentadienyl, 1,2,4-trimethylcyclopentadienyl,pentamethylcyclopentadienyl, and trimethylsilylcyclopentadienyl groups.Examples of R¹¹ to R¹³ in formulae (II-8) to (II-10) area halogen atomsuch as fluorine, chlorine, bromine and iodine atoms; an alkyl grouphaving from 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl,isopropyl, n-butyl, octyl and 2-ethylhexyl groups; an alkoxy grouphaving from 1 to 20 carbon atoms, such as methoxy, ethoxy, propoxy,butoxy and phenoxy groups; an aryl, alkylaryl or arylalkyl group havingfrom 6 to 20 carbon atoms, such as phenyl, tolyl, xylyl and benzylgroups; an acyloxy group having from 1 to 20 carbon atoms, such asheptadecylcarbonyloxy group; and a silicon-containing substituent suchas trimethylsilyl and trimethylsilylmethyl groups. The Lewis base forthese includes, for example, ethers such as dimethyl ether, diethylether, tetrahydrofuran; thioethers such as tetrahydrothiophene; esterssuch as ethyl benzoate; nitriles such as acetonitrile, benzonitrile;amines such as trimethylamine, triethylamine, tributylamine,N,N-dimethylaniline, pyridine, 2,2′-bipyridine, phenanthroline; andphosphines such as triethylphosphine, triphenylphosphine. The linearunsaturated hydrocarbon for these includes, for example, ethylene,butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and theirderivatives; and the cyclic unsaturated hydrocarbon includes, forexample, benzene, toluene, xylene, cycloheptatriene, cyclooctadiene,cyclooctatriene, cyclooctatetraene, and their derivatives. Thecovalent-bonding linking group for A in formula (II-10) includes, forexample, methylene crosslinking, dimethylmethylene crosslinking,ethylene crosslinking, 1,1′-cyclohexylene crosslinking, dimethylsilylenecrosslinking, dimethylgermylene crosslinking, and dimethylstannylenecrosslinking.

Examples of the compounds of formula (II-8) are(pentamethylcyclopentadienyl)trimethylzirconium,(pentamethylcyclopentadienyl)triphenylzirconium,(pentamethylcyclopentadienyl)tribenzylzirconium,(pentamethylcyclopentadienyl)trichlorozirconium,(pentamethylcyclopentadienyl)trimethoxyzirconium,(cyclopentadienyl)trimethylzirconium.

Examples of the compounds of formula (II-9) arebis(cyclopentadienyl)dimethylzirconium,bis(cyclopentadienyl)diphenylzirconium,bis(cyclopentadienyl)diethylzirconium,bis(cyclopentadienyl)dibenzylzirconium,bis(cyclopentadienyl)dimethoxyzirconium,bis(cyclopentadienyl)dichlorozirconium.

Examples of the compounds of formula (II-10) arerac-dimethylsilanediyl-bis-1-(2-methyl-4,5-benzoindenyl)-zirconiumdichloride, rac-ethanediyl-bis-1-(2-methyl-4,5-benzoindenyl)-zirconiumdichloride, rac-dimethylsilanediyl-bis-1-(4,5-benzoindenyl)-zirconiumdichloride,rac-dimethylsilanediyl-bis-1-(2-methyl-4-phenylindenyl)-zirconiumdichloride,rac-dimethylsilanediyl-bis-1-[2-methyl-4-(1-naphthyl)indenyl]-zirconiumdichloride.

The above (iv) includes transition metal compounds of the followinggeneral formula (II-11) and their derivatives.

wherein M⁶ represents a titanium, zirconium or hafnium atom; CPrepresents a cyclic unsaturated hydrocarbon group or a linearunsaturated hydrocarbon group, such as a cyclopentadienyl group, asubstituted cyclopentadienyl group, an indenyl group, a substitutedindenyl group, a tetrahydroindenyl group, a substitutedtetrahydroindenyl group, a fluorenyl group or a substituted fluorenylgroup; X³ represents a hydrogen atom, a halogen atom, an alkyl grouphaving from 1 to 20 carbon atoms, an aryl, alkylaryl or arylalkyl grouphaving from 6 to 20 carbon atoms; Z represents SiR¹⁴ ₂, CR¹⁴ ₂, SiR¹⁴₂SiR¹⁴ ₂, CR¹⁴ ₂CR¹⁴ ₂, CR¹⁴ ₂CR¹⁴ ₂ CR¹⁴ ₂═CR¹⁴, CR¹⁴ ₂SiR¹⁴ ₂ or GeR¹⁴₂; Y¹ represents —N(R¹⁵)—, —O—, —S—, or —P(R¹⁵)—; R¹⁴ represents ahydrogen atom, or an alkyl, aryl, silyl, halogenoalkyl or halogenoarylgroup having at most 20 non-hydrogen atoms, or is a combination of suchgroups; R¹⁵ represents an alkyl group having from 1 to 10 carbon atoms,or an aryl group having from 6 to 10 carbon atoms, or it may form aclosed ring system along with one or more R¹⁴'s and at most 30non-hydrogen atoms; and w indicates 1 or 2.

Examples of the compounds of formula (II-11) are (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediylzirconium dichloride,(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitaniumdichloride,(methylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediylzirconiumdichloride, (methylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitanium dichloride.

The above (v) includes transition metal compounds of the followinggeneral formula (II-12) and their derivatives.

wherein M⁶ represents a titanium, zirconium or hafnium atom; C_(p)represents a ligand selected from a cyclopentadienyl group, asubstituted cyclopentadienyl group, an indenyl group, a substitutedindenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an amido group, a phosphido group, ahydrocarbon group and a silicon-containing group, and this forms acrosslinked structure via A¹ and A²; two C_(p)'s may be the same ordifferent; X⁴ represents a σ-bonding ligand; plural X⁴'s, if any, may bethe same or different, and may be crosslinked with other X⁴, C_(p) ory²; y² represents a Lewis base; plural y²'s, if any, may be the same ordifferent, and may be crosslinked with other y², C_(p) or X⁴; A¹ and A²each are a divalent crosslinking group that bonds the two ligands,representing a hydrocarbon group having from 1 to 20 carbon atoms, ahalogen-containing hydrocarbon group having from 1 to 20 carbon atoms, asilicon-containing group, a germanium-containing group, a tin-containinggroup, —O—, —CO—, —S—, —SO₂—, —NR¹⁶—, —PR¹⁶—, —P(O)R¹⁶—, —BR¹⁶—, or—AlR¹⁶—; R¹⁶ represents a hydrogen atom, a halogen atom, a hydrocarbongroup having from 1 to 20 carbon atoms, or a halogen-containinghydrocarbon group having from 1 to 20 carbon atoms; A¹ and A² may be thesame or different; 1 is an integer of from 1 to 5, indicating [(atomicvalency of M⁶)−2]; and r is an integer of from 0 to 3.

In the transition metal compounds of formula (II-12) (hereinafterreferred to as double-crosslinked complexes), M⁶ is titanium, zirconiumor hafnium, and is preferably zirconium or hafnium. As so mentioned inthe above, C_(p) represents a ligand selected from a cyclopentadienylgroup, a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a heterocyclopentadienyl group, a substitutedheterocyclopentadienyl group, an amido group (—N<), a phosphido group(—P<), a hydrocarbon group (>CR¹⁷—, >C<), and a silicon-containing group(>SiR¹⁷—, >C<) (in which R¹⁷ represents a hydrogen atom, a hydrocarbongroup having from 1 to 20 carbon atoms, or a hetero atom-containinggroup), and this C_(p) forms a crosslinked structure via A¹ and A²; andtwo C_(p)'s may be the same or different. C_(p) is preferably acyclopentadienyl group, a substituted cyclopentadienyl group, an indenylgroup or a substituted indenyl group.

Examples of the σ-bonding ligand for X⁴ are a halogen atom, ahydrocarbon group having from 1 to 20 carbon atoms, an alkoxy grouphaving from 1 to 20 carbon atoms, an aryloxy group having from 6 to 20carbon atoms, an amido group having from 1 to 20 carbon atoms, asilicon-containing group having from 1 to 20 carbon atoms, a phosphidogroup having from 1 to 20 carbon atoms, a sulfido group having from 1 to20 carbon atoms, and an acyl group having from 1 to 20 carbon atoms.Plural X⁴'s, if any, may be the same or different, and may becrosslinked with other X⁴, C_(p) or y².

Examples of the Lewis base for y² are amines, ethers, phosphines, andthioethers. Plural y²'S, if any, may be the same or different, and maybe crosslinked with other y², C_(p) or X⁴.

Preferably, at least one crosslinking group of A¹ and A² is ahydrocarbon group. For example, it is represented by:

wherein R¹⁸ and R¹⁹ each represent a hydrogen atom, or a hydrocarbongroup having from 1 to 20 carbon atoms, and these may be the same ordifferent, and may be bonded to each other to form a cyclic structure;and e indicates an integer of from 1 to 4.

Examples of the group are a methylene group, an ethylene group, anethylidene group, a propylidene group, an isopropylidene group, acyclohexylidene group, a 1,2-cyclohexylene group, and a vinylidene group(CH₂═C═). Of those, preferred are a methylene group, an ethylene groupand an isopropylidene group. A¹ and A² may be the same or different.

In the transition metal compounds of formula (II-12) in which C_(p) is acyclopentadienyl group, a substituted cyclopentadienyl group, an indenylgroup or a substituted indenyl group, the crosslinking bond of A¹ and A²may be either a (1,1′)(2,2′)-double-crosslinking bond or a(1,2′)(2,1′)-double-crosslinking bond. Of the transition metal compoundsof formula (II-12) of the type, preferred are those of the followinggeneral formula (II-12a) having, as the ligand, a double-crosslinkedbiscyclopentadienyl derivative.

In formula (II-12a), M⁶, A¹, A², q and r have the same meanings asabove. X⁴ represents a σ-bonding ligand, and plural X⁴'s, if any, may bethe same or different, and may be crosslinked with other X⁴ or Y². Forexamples of X⁴ in formula (II-12a), referred to are the same as thosementioned hereinabove for X⁴ in formula (II-12). Y² represents a Lewisbase, and plural Y²'s, if any, may be the same or different, and may becrosslinked with other Y² or X⁴. For examples of Y² in formula (II-12a),referred to are the same as those mentioned hereinabove for Y² informula (II-12). R²⁰ to R²⁵ each represent a hydrogen atom, a halogenatom, a hydrocarbon group having from 1 to 20 carbon atoms, ahalogen-containing hydrocarbon group having from 1 to 20 carbon atoms, asilicon-containing group, or a hetero atom-containing group, but atleast one of them must not be a hydrogen atom. R²⁰ to R²⁵ may be thesame or different, and the neighboring groups of these may be bonded toeach other to form a ring.

In the transition metal compounds having a ligand of such adouble-crosslinked biscyclopentadienyl derivative, the ligand may be inany form of (1,1′)(2,2′)-double-crosslinking or(1,2′)(2,1′)-double-crosslinking. Examples of the transition metalcompounds of formula (II-12) are(1,1′-ethylene)(2,2′-ethylene)-bis(indenyl)zirconium dichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(indenyl)zirconium dichloride,(1,1′-methylene) (2,2′-methylene)-bis (indenyl) zirconium dichloride,(1,2′-methylene)(2,1′-methylene)-bis(indenyl)zirconium dichloride,(1,1′-isopropylidene)(2,2′-isopropylidene)-bis(indenyl)zirconiumdichloride,(1,2′-isopropylidene)(2,1′-isopropylidene)-bis(indenyl)zirconiumdichloride, (1,1′-ethylene)(2,2′-ethylene)-bis(3-methylindenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-ethylene)-bis(3-methylindenyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-ethylene)-bis(4,5-benzoindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(4,5-benzoindenyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-ethylene)-bis(4-isopropylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(4-isopropylindenyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-ethylene)-bis(5,6-dimethylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(5,6-dimethylindenyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-ethylene)-bis(4,7-diisopropylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(4,7-diisopropylindenyl)zirconiumdichloride, (1,1′-ethylene)(2,2′-ethylene)-bis(4-phenylindenyl)zirconiumdichloride,(1,2′-ethylene)((2,1′-ethylene)-bis(4-phenylindenyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-ethylene)-bis(3-methyl-4-isopropylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(3-methyl-4-isopropylindenyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-ethylene)-bis(5,6-benzoindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(5,6-benzoindenyl)zirconiumdichloride, (1,1′-ethylene)(2,2′-isopropylidene)-bis(indenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-isopropylidene)-bis(indenyl)zirconiumdichloride, (1,1′-isopropylidene)(2,2′-ethylene)-bis(indenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-ethylene)-bis(indenyl)zirconiumdichloride, (1,1′-methylene)(2,2′-ethylene)-bis(indenyl)zirconiumdichloride, (1,1′-ethylene)(2,2′-methylene)-bis(indenyl)zirconiumdichloride, (1,1′-methylene)(2,2′-isopropylidene)-bis(indenyl)zirconiumdichloride, (1,2′-methylene)(2,1′-isopropylidene)-bis(indenyl)zirconiumdichloride, (1,1′-isopropylidene)(2,2′-methylene)-bis(indenyl)zirconiumdichloride,(1,1′-methylene)(2,2′-methylene)(3-methylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride,(1,1′-isopropylidene)(2,2′-isopropylidene)(3-methylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride,(1,1′-propylidene)(2,2′-propylidene)(3-methylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-methylene)-bis(3-methylcylopentadienyl)zirconiumdichloride,(1,1′-methylene)(2,2′-ethylene)-bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,1′-isopropylidene)(2,2′-ethylene)-bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-isopropylidene)-bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,1′-methylene)(2,2′-methylene)-bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,1′-methylene)(2,2′-isopropylidene)-bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,1′-isopropylidene)(2,2′-isopropylidene)-bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-methylene)-bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-isopropylidene)-bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,1′-methylene)(2,2′-methylene)-bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,1′-methylene)(2,2′-isopropylidene)-bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,1′-isopropylidene)(2,2′-isopropylidene)-bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-methylene)-bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-isopropylidene)-bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-methylene)-bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-isopropylidene)-bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,2′-isopropylidene)(2,1′-isopropylidene)-bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-methylene)-bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-isopropylidene)-bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-methylene)-bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-isopropylidene)-bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-isopropylidene)(2,1′-isopropylidene)-bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride, and their derivatives in which zirconium is replaced withtitanium or hafnium. For the component (A), two or more of the compoundsmay be used as combined.

The component (B) (components (B-1) and (B-2)) may be the same as thecomponent (B) (components (B-1) and (B-2)) to be in the catalyst for themacromonomer production mentioned above.

Like that for the macromonomer production, the catalyst for the graftcopolymer production in the invention comprises the component (A), thecomponent (B) and optionally an organoaluminium compound for thecomponent (C), and the catalyst components may be held on a carrier ormay be subjected to prepolymerization before use. For the details of thecatalyst for the graft copolymer production, referred to are the same asthose mentioned hereinabove.

In producing the propylene graft copolymer of the invention, aZiegler-Natta catalyst may also be used. For the details of theZiegler-Natta catalyst, referred to are the same as those mentioned inthe section of the first aspect of the invention.

The comonomer for producing the graft copolymer of the inventionincludes ethylene, propylene, α-olefins having from 4 to 20 carbonatoms, cyclic olefins and styrenes such as those mentioned hereinabove.The copolymerization may be effected in the same manner and under thesame condition as those mentioned hereinabove. In the invention, one andthe same or two or more different types of the above-mentioned propylenemacromonomer [1] may be copolymerized with the comonomer, either singlyor as combined in any desired ratio. Different types of the macromonomer[1], if combined for copolymerization, may be blended in a mode ofsolution blending or powder blending, or may be directly blended in areactor. Preferably, the polymerization condition to be employed in theinvention is such that the resulting copolymer may have a highermolecular weight, for which, for example, the monomer concentration isincreased.

The method for producing the propylene graft copolymer of the inventionis described more concretely. The macromonomer component is firstprepared, then this is transferred into a separate polymerizationreactor while the catalytic activity is not still lost, and this iscopolymerized with the comonomer therein (two-stage polymerization).Alternatively, the copolymerization may be effected in a polymerizationreactor that differs from the polymerization reactor in which themacromonomer component is prepared through polymerization. In any ofsuch two-stage polymerization (or more multi-stage polymerization) orseparate line polymerization as above, the condition of reactiontemperature and reaction pressure may be the same as that for thepolymerization to prepare the macromonomer component. For the secondstage polymerization in the two-stage polymerization process, a freshcatalyst may be or may not be added to the system after the first stagepolymerization. According to the process, obtained are, for example,APP-g-APP, IPP-g-IPP and SPP-g-SPP, for which both the first and secondstages of the process are for homopolymerization. For these, X-g-Yindicates that X and Y are grafted. In the process, when suitablecatalyst components are combined to prepare a metallocene catalyst andwhen the thus-prepared metallocene catalyst is used, various types ofgraft copolymers can be obtained, including, for example, graftcopolymers of which the main chain and the side chains have the samestereospecificity, and graft copolymers of which the main chain differsfrom the side chains in point of the stereospecificity, such asAPP-g-IPP, APP-g-SPP, IPP-g-SPP. According to the process, also producedare IPP-g-PE, APP-g-PE, SPP-g-PE and the like in which PE indicatespolyethylene. Further produced are IPP-g-(P-co-E), in which (P-co-E)indicates copolymerization (-co-) of propylene (P) and ethylene (E); aswell as those in which ethylene (E) is replaced with any of α-olefinshaving from 4 to 20 carbon atoms such as butene, hexane, octene or thelike, or with any of styrene derivatives or cyclic olefins, and those inwhich IPP is replaced with any of APP or SPP. Examples of the propylenegraft copolymer are shown in the following matrix, marked with “O”.

TABLE II-1 Main Chain P-co-E P-co-C₄₋₂₀ P-co-Cy P-co-St E-co-C₄₋₂₀E-co-Cy Side P-co-E 0 0 0 0 0 0 Chains P-co-C₄₋₂₀ 0 0 0 0 0 P-co-Cy 0 00 0 P-co-St 0 0 0 P-co-E: propylene-ethylene copolymer P-co-C₄₋₂₀:propylene-C₄₋₂₀ α-olefin copolymer P-co-Cy: propylene-cyclic olefincopolymer P-co-St: propylene-styrene copolymer E-co-C₄₋₂₀: ethyleneC₄₋₂₀ α-olefin copolymer E-co-Cy: ethylene-cyclic olefin copolymer

In the invention, both the first and second steps may be effected in thepresence of a metallocene catalyst, or the second step may be effectedin the presence of a Ziegler-Natta catalyst.

[3] Olefin Resin Composition:

The olefin resin composition of the invention comprises 100 parts byweight of a thermoplastic resin and from 0.05 to 70 parts by weight ofthe above-mentioned propylene macromonomer [1] or propylene graftcopolymer [2]. Preferably, it comprises 100 parts by weight of athermoplastic resin and from 0.1 to 65 parts by weight, more preferablyfrom 0.2 to 60 parts by weight, even more preferably from 0.3 to 50parts by weight, most preferably from 0.35 to 40 parts by weight of theabove-mentioned propylene macromonomer [1] or olefin graft copolymer[2]. If the amount of the macromonomer [1] or the copolymer [2] servingas a compatibilizer is smaller than 0.05 parts by weight in the resincomposition, the absolute amount of the compatibilizer is not enough andthe compatibilizer will be ineffective for improving thephysical-properties of the resin composition. However, if its amount islarger than 70 parts by weight, the propylene macromonomer [1] or thepropylene graft copolymer [2] is to be the main ingredient of the resincomposition, and, if so, the macromonomer [1] or the copolymer [2] couldnot serve as a compatibilizer in the resin composition. In the olefinresin composition of the invention, any of the propylene macromonomer[1] or the propylene graft copolymer [2] may be used. Preferably,however, the resin composition contains the propylene graft copolymer[2].

The thermoplastic resin to be in the resin composition includes, forexample, polyolefin resins, polystyrene resins, condensed polymershaving an increased molecular weight, and polymers produced throughaddition polymerization and having an increased molecular weight.Examples of the polyolefin resins are high-density polyethylene,low-density polyethylene, poly-3-methylbutene-1, poly-4-methylpentene-1;linear low-density polyethylene copolymerized with any of butene-1,hexene-1, octene-1,4-methylpentene-1, or 3-methylbutene-1; saponifiedethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer,ethylene-acrylate copolymer, ethylene ionomer, and polypropylene.Examples of the polystyrene resins are general polystyrene, isotacticpolystyrene, and high-impact polystyrene (modified with rubber).Examples of the condensed polymers having an increased molecular weightare polyacetal resin, polycarbonate resin; polyamide resin such as nylon6 and nylon 6·6; polyester resin such as polyethylene terephthalate andpolybutylene terephthalate; polyphenylene-oxide resin, polyimide resin,polysulfone resin, polyether-sulfone resin, and polyphenylene-sulfideresin. Examples of the polymers produced through addition polymerizationand having an increased molecular weight are polymers of polar vinylmonomers, and polymers of diene monomers, concretely, polymethylmethacrylate, polyacrylonitrile, acrylonitrile-butadiene copolymer,acrylonitrile-butadiene-styrene copolymer, diene polymer in which thediene chain is hydrogenated, and thermoplastic elastomer.

In the olefin resin composition of the invention, one preferredcombination of thermoplastic resins is a polyolefin—polyolefincombination. For example, it includes a combination of polypropylene andpolyethylene such as LLDPE, LDPE or HDPE; a combination of polypropyleneand a soft olefin polymer such as ethylene/propylene copolymer,thermoplastic elastomer, EPDM or EPR; a combination of polyethylene anda soft olefin polymer such as ethylene/propylene copolymer,thermoplastic elastomer, EPDM or EPR; a combination of polypropylene andpolystyrene such as APS, IPS or SPS; a combination of polypropylene andpropylene/α-olefin copolymer; a combination of polyethylene andpolystyrene such as APS, IPS or SPS; a combination of polyethylene andethylene/α-olefin copolymer; a combination of propylene/α-olefincopolymer and polystyrene such as APS, IPS or SPS; a combination ofethylene/α-olefin copolymer and polystyrene such as APS, IPS or SPS; acombination of ethylene/styrene copolymer and polypropylene resin; and acombination of ethylene/styrene copolymer and polyethylene resin. To thecomposite resin system as above, added is the propylene macromonomer [1]or the propylene graft copolymer [2] serving as a compatibilizer, andthe mechanical properties of the resulting resin composition areimproved.

Preferably, the olefin resin composition of the invention is such thatthe relaxation rate of the long-term relaxation component therein,measured through solid ¹H-NMR, (1/R₁) falls between 1.0 and 2.0 (1/sec),more preferably between 1.2 and 1.8 (1/sec), even more preferablybetween 1.3 and 1.6 (1/sec). Also preferably, the olefin resincomposition of the invention is such that the ratio of the relaxationrate (1/R₁) to the relaxation rate (1/R₁)₀ of the long-term relaxationcomponent, measured through solid ¹H-NMR, of a resin compositioncontaining neither the propylene macromonomer nor the propylene graftcopolymer, [(1/R₁)/(1/R₁)₀], satisfies the following relationship:[(1/R ₁)/(1/R ₁)₀]≧1.01.Satisfying it, the resin compatibility in the composition is good.More preferably, the ratio satisfies;[(1/R ₁)/(1/R ₁)₀]≧1.02,even more preferably,[(1/R ₁)/(1/R ₁)₀]≧1.03.

In the invention, the values (1/R₁) and (1/R₁)₀ of the resincompositions are measured according to a method of inversion recovery(180°-τ-90°, pulse process), using a solid ¹H-NMR device mentionedbelow.

-   -   Device: BRUKER's CPX-90    -   Nucleus to be measured: hydrogen nucleus (¹H)    -   Frequency: 90 MHz    -   Temperature: 30° C.    -   90° pulse width: 2.4 to 2.5 microseconds

For producing the olefin resin composition of the invention, employableis a melt blending method or a solution blending method. If desired, anantioxidant (e.g., BHT) may be added to the composition.

The invention is described in more detail with reference to thefollowing Examples, which, however, are not intended to restrict thescope of the invention.

First mentioned are the methods for analyzing and evaluating themacromonomer, the graft copolymer and the resin composition of theinvention.

(1) “Analysis of Macromonomer”

<1> Measurement through ¹H-NMR:

The terminal structure of each sample is measured under the conditionmentioned below. The result is shown in Table II-2.

-   -   Device: JEOL's JNM-LA500    -   Frequency: 10000 Hz    -   Pulse width: 2.9 μsec (450)    -   Pulse repetition time: 9 sec    -   Integration frequency: 500 times    -   Solvent: 1,2,4-trichlorobenzene/heavy benzene (9/1 by volume)    -   Temperature: 130° C.

The spectral pattern has peaks based on the terminal vinyl group at 5.8ppm and 5.0 ppm, and a minor peak based on the terminal vinylidene groupat 4.7 ppm. The ratio of the terminal vinyl group to all the terminalunsaturated groups is calculated, and it indicates the vinyl selectivityof the sample.

<2> Measurement of Weight-average Molecular Weight (Mw) through GPC:

The weight-average molecular weight (Mw) of each sample is measuredunder the condition mentioned below.

-   -   Device: Waters 150C        -   Detector, RI        -   Columns (two), Shodex UT-806M    -   Condition: Solvent: TCB        -   Temperature; 145° C.        -   Flow Rate: 1.0 ml/min        -   Sample Concentration: 0.2%        -   Calibration Curve: Universal Calibration            <3> Monomer Composition Analysis:

From the monomer-based peak intensity in the ¹H-NMR spectral pattern,the monomer composition is determined in an ordinary manner.

(2) “Analysis of Graft Copolymer”

<1> Measurement of Macromonomer Content:

According to the method <1> for “Analysis of Macromonomer” mentionedabove, each graft copolymer sample is analyzed through ¹H-NMR, and themacromonomer content of the graft copolymer is calculated from thecompositional ratio of propylene/ethylene in the graft copolymer and thecompositional ratio of propylene/ethylene in the macromonomer.

<2> Measurement of Intrinsic Viscosity [η]:

In a solvent decalin at 135° C., the intrinsic viscosity [η] of eachsample is measured, and corrected according to the Huggins' viscosityequation in which the Huggins' constant is 0.35.

<3> Measurement of Molecular Weight Distribution (Mw/Mn):

Each sample is analyzed according to the method <1> for “Analysis ofMacromonomer” mentioned above, and its molecular weight distribution iscalculated from the data.

<4> Melting Point:

Using a differential scanning calorimeter (Parkin Elmer's DSC-7), 10 mgof each sample is heated and melted in a nitrogen atmosphere at 230° C.for 3 minutes, then cooled to 0° C. at a cooling rate of 10° C./min,kept at 0° C. for 3 minutes, and thereafter again heated at a heatingrate of 10° C./min. The peak top of the highest peak in the endothermiccurve of the sample melt is read, and this is the melting point (° C.)of the sample.

(3) “Analysis of Olefin Resin Composition”

<1> In a solvent decalin at 135° C., the intrinsic viscosity [η] of eachsample of olefin resin compositions is measured, and corrected accordingto the Huggins' viscosity equation in which the Huggins' constant is0.35.

<2> Using a solid ¹H-NMR device mentioned below, the relaxation rate ofthe long-term relaxation component of each sample of resin compositions,(1/T₁) and (1/T₁)₀, was measured according to a method of inversionrecovery (180°-τ-90°, pulse process).

-   -   Device: BRUKER's CPX-90    -   Nucleus to be measured: hydrogen nucleus (¹H)    -   Frequency: 90 MHz    -   Temperature: 30° C.    -   90° pulse width: 2.4 to 2.5 microseconds

Measured through DSC and solid ¹H-NMR (solid echo process), the degreeof crystallization was the same between PP and HDPE.

EXAMPLE II-1 Production of Propylene/ethylene Copolymerized Macromonomer

(1) Synthesis of(pentamethylcyclopentadienyl)(tetramethylcyclopentadienyl)-zirconiumdichloride:

10.0 g (33.6 mmols) of (pentamethylcyclopentadienyl)zirconiumtrichloride, and 150 ml of tetrahydrofuran were put into a 300-mltwo-neck egg-plant flask. To this, dropwise added was a tetrahydrofuransolution (50 ml) of 4.3 g (33.6 mmols) of (tetramethylcyclopentadienyl)lithium that had been separately prepared at 0° C. This was warmed up toroom temperature, and then stirred as such for 8 hours. The solvent wasevaporated away, and the residue was extracted in 100 ml ofdichloromethane. The resulting extract was concentrated and cooled to−20° C. to obtain 5.8 g of(pentamethylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride. A part of this was collected and dissolved in dewateredtoluene to prepare a catalyst solution having a concentration of 10μmols/ml.

(2) Production of Copolymerized Macromonomer:

In a nitrogen atmosphere, 1000 ml of dewatered toluene, 10 mmols (interms of Al) of ALBEMARLE's methylaluminoxane, and 10 μmols of the(pentamethylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride prepared in the above (1) were put into a 2-liter stainlesspressure autoclave equipped with a stirrer. With stirring, this washeated up to 40° C. Propylene at a rate of 10 normal liters/min andethylene at a rate of 0.5 normal liters/min were continuously fed intothe autoclave, and the total pressure of the reaction system was kept at0.5 MPa (gauge). In that condition, the monomers were copolymerized for60 minutes.

After the reaction, the autoclave was degassed and opened, and thereaction mixture was taken out and put into a large amount of methanolto wash the macromonomer. The viscous macromonomer was collected, anddried under reduced pressure at 80° C. for 30 hours. The yield of thepropylene-ethylene copolymerized macromonomer obtained was 68.4 g. Thiswas analyzed according to the above-mentioned “Analysis ofMacromonomer”, and its data are shown in Table II-2.

EXAMPLE II-2 Production of Propylene/ethylene Copolymerized Macromonomer

(1) Production of Copolymerized Macromonomer:

In the same manner as in Example II-1 (2), 37 g of a propylene/ethylenecopolymerized macromonomer was obtained, for which, however, the feedrate of ethylene was 0.2 normal liters/min.

(2) Analysis of Copolymerized Macromonomer:

The macromonomer was analyzed in the same manner as in Example II-1, andits data are shown in Table II-2.

EXAMPLE II-3 Production of Propylene Macromonomer

(1) Preparation of Aluminoxane:

For use herein, methylaluminoxane was processed in the following manner.

1.0 liter of a toluene solution of methylaluminoxane (1.5 mols/liter,from ALBEMARLE, containing 14.5% by weight of trimethylaluminium) wasvaporized under reduced pressure (10 mmHg) at 60° C. to remove thesolvent, and then dried up. In this condition, this was kept as it wasfor 4 hours, and then cooled to room temperature to obtain dry-upmethylaluminoxane. The dry-up methylaluminoxane was re-dissolved indewatered toluene added thereto, to thereby restore its volume to theoriginal before solvent removal. Then, the trimethylaluminium content ofthe methylaluminoxane solution was determined through ¹H-NMR, and was3.6% by weight. The total aluminium content of the methylaluminoxanesolution was measured according to a fluorescent X-ray (ICP) method, andwas 1.32 mols/liter. Then, the solution was statically left as it wasfor 2 full days to thereby make the insoluble component depositedtherein. The supernatant was filtered through a G5 glass filter in anitrogen atmosphere to recover the filtrate. This is methylaluminoxane(a) for use herein. Its concentration measured through ICP was 1.06.From the thus-processed methylaluminoxane, 10.9% by weight oforganoaluminium and 17.3% by weight of the insoluble component wereremoved.

(2) Preparation of Carrier for Olefin Polymerization Catalyst:

27.1 g of SiO₂ (Fuji Silicia Chemical's P-10) was dried under reducedpressure at 200° C. for 4.0 hours in a slight nitrogen atmosphere, and25.9 g of dry SiO₂ was obtained. The dry SiO₂ was put into 400 ml ofdewatered toluene that had been previously cooled to −78° C. in a bathof dry ice/methanol, and stirred. With still stirring, 145.5 ml of atoluene solution of the methylaluminoxane (a) prepared in the above (1)was dropwise added to the toluene suspension of SiO₂, over a period of 2hours all through a dropping funnel.

Next, this was stirred for 4.0 hours, and then warmed from −78° C. up to20° C. over a period of 6 hours, and this was kept in this condition for4.0 hours. Next, this was heated from 20° C. up to 80° C. over a periodof 1 hour, and then left at 80° C. for 4.0 hours to thereby complete thereaction of silica and methylaluminoxane therein. The resultingsuspension was filtered at 80° C., and the solid thus obtained waswashed twice with 400 ml of dewatered toluene at 60° C. and then twicewith 400 ml of dewatered n-heptane at 60° C. After thus washed, thesolid was dried under reduced pressure at 60° C. for 4.0 hours, and33.69 g of SiO₂-held methylaluminoxane was obtained. This serves as acarrier for olefin polymerization catalyst. The proportion ofmethylaluminoxane held on SiO₂ was 30.1% per gram of SiO₂.

To all the thus-obtained, SiO₂-held methylaluminoxane, added wasdewatered n-heptane to make 500 ml. The methylaluminoxane concentrationin the suspension thus obtained herein was 0.27 mols/liter.

(3) Preparation of Catalyst Component:

2.0 mmols (7.41 ml) of the SiO₂-held methylaluminoxane prepared in theabove (2) was put into a 50-ml container that had been purged with drynitrogen, to which was added 20 ml of dewatered toluene and stirred. Tothe resulting suspension, added was 1.0 ml (10 μmols) of the toluenesolution of(pentamethylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride prepared in Example II-1, and kept stirred at roomtemperature for 0.5 hours. Stirring it was stopped, and the solidcatalyst component was deposited. The thus-deposited solid catalystcomponent was found red and the solution was colorless transparent. Thesolution was removed through decantation, 20 ml of n-heptane was addedto the residue, and an SiO₂-held metallocene catalyst slurry was thusobtained.

(4) Production of Polymer:

In a nitrogen atmosphere, 1000 ml of dewatered toluene, 0.5 mmols oftriisobutylaluminium (TIBA), and 10 μmols, in terms of zirconium, of thecarrier-held catalyst prepared in the above (3) were put into a 2-literstainless pressure autoclave equipped with a stirrer. This was stirredand kept at 15° C. Propylene to have a pressure of 0.8 MPa (gauge) wasintroduced into it for 120 minutes and polymerized into a polymer.

After the reaction, the autoclave was degassed and opened, and thereaction mixture was taken out and put into a large amount of methanolto wash the macromonomer. The viscous macromonomer was collected, anddried under reduced pressure at 80° C. for 30 hours. The yield of thepropylene macromonomer obtained was 45 g.

(5) Analysis of Macromonomer:

This was analyzed in the same manner as in Example II-1, and its dataare shown in Table II-2.

In the Table, “Example 1” means “Example II-1”, and the same shall applyto all the other Examples and Comparative Examples.

TABLE II-2 Details Example 1 Example 2 Example 3 Resin PropertiesTerminal Vinyl Selectivity 95.4 95.5 91.7 (%) Mw 1280 1010 2500Propylene Content (mol %) 63 82 100 Ethylene Content (mol %) 37 18 0

EXAMPLE II-4 Production of Graft Copolymer:

(1) Preparation of Catalyst Component:

A catalyst component was prepared in the same manner as in Example II-3(3), for which, however, used was 5 μmols ofracemi-dimethylsilyldiyl-bis[2-methyl-4-phenylindenyl]zirconiumdichloride [rac-Me₂Si-(2Me-4-Ph-Ind)₂ZrCl₂] in place of 10 μmols of(pentamethylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride.

(2) Production of Graft Copolymer:

10 g of the macromonomer produced in Example II-1 (2) was dissolved intoluene, and bubbled with nitrogen to attain complete oxygen removal andwater removal from it. In a nitrogen atmosphere, 200 ml of the heptanesolution of the macromonomer, 0.5 mmols of triisobutylaluminium (TIBA),and 5 μmols, in terms of zirconium, of the carrier-held catalystprepared in the above (1) were put into a 1.6-liter stainless pressureautoclave equipped with a stirrer. This was stirred and kept at 60° C.Propylene to have a pressure of 0.6 MPa (gauge) was introduced into itfor 120 minutes and polymerized into a polymer.

After the reaction, the autoclave was degassed and opened, and thereaction mixture was taken out and filtered to recover the graftcopolymer. This was washed repeatedly four times with a large amount ofheptane to remove the non-reacted macromonomer. The thus-washed graftcopolymer was dried under reduced pressure at 80° C. for 6 hours. Theyield of the copolymer was 30 g. This was analyzed according to“Analysis of Graft Copolymer” mentioned above, and its data are shown inTable II-3.

EXAMPLE II-5 Production of Graft Copolymer:

In the same manner as in Example II-4, produced was an ethylene graftcopolymer; for which, however, 10 g of the macromonomer produced inExample II-3 (4) was used, and ethylene and not propylene was introducedinto the system to have a pressure of 0.1 MPa (gauge) with 30 ml ofhydrogen added thereto. The yield of the graft copolymer was 45 g. Thiswas analyzed in the same manner as in Example II-4, according to“Analysis of Graft Copolymer” mentioned above, and its data are shown inTable II-3.

EXAMPLE II-6 Production of Graft Copolymer

In the same manner as in Example II-4, produced was a graft copolymer,for which, however, 10 g of the macromonomer produced in Example II-3was used. The yield of the graft copolymer was 40 g. This was analyzedin the same manner as in Example II-4, according to “Analysis of GraftCopolymer” mentioned above, and its data are shown in Table II-3.

TABLE II-3 Details Example 4 Example 5 Example 6 Intrinsic Viscosity [η](dl/g) 2.68 1.66 2.55 Macromonomer Content (wt. %) 0.2 0.5 0.2 Mw/Mn 2.12.0 1.8 Melting Point (° C.) 146 132 146

EXAMPLE II-7 Production of Resin Composition

(1) Preparation of Resin Composition:

A polymer comprised of 90% by weight of IPP mentioned below and 10% byweight of APP also mentioned below, and containing 5.0 parts by weight,relative to the total weight of these IPP and APP, of the graftcopolymer that had been prepared in Example II-4 was dissolved underheat in xylene containing 4000 ppm of an antioxidant, BHT. The resultingmixture was re-precipitated in a large amount of methanol, and dried toprepare a resin composition.

IPP:

This is isotactic polypropylene prepared by polymerizing polypropylenein a solvent heptane in the presence ofracemi-dimethylsilyldiyl-bis[2-methyl-4-phenylindenyl]zirconiumdichloride, rac-Me₂Si-[2-Me-4-Ph-Ind]₂ZrCl₂, and methylaluminoxane(MAO). Its intrinsic viscosity [η] is 2.76 dl/g; and its melting pointis 148° C.

APP:

This is atactic polypropylene prepared by polymerizing propylene in asolvent toluene in the presence of a catalyst CP*Me₂Si(tBuN)TiCl₂/MAO(so-called CGC catalyst). Its intrinsic viscosity [η] is 3.10 dl/g.

(2) Analysis of Olefin Resin Composition:

The resin composition was analyzed according to “Analysis of OlefinResin Composition” mentioned above, and its data are shown in TableII-4.

EXAMPLE II-8 Production of Resin Composition:

A resin composition was produced in the same manner as in Example II-7,for which, however, used was 1.0 part by weight of the graft copolymerprepared in Example II-4. Its data are shown in Table II-4.

COMPARATIVE EXAMPLE II-1 Production of Resin Composition

A resin composition was produced in the same manner as in Example II-7,for which, however, the graft copolymer of a Example II-4 was not used.Its data are shown in Table II-b 4.

EXAMPLE II-9 Production of Resin Composition

A polymer comprised of 90% by weight of the same APP as that used inExample II-7 and 10% by weight of Idemitsu Petrochemical's HDPE (grade440M), and containing 5.0 parts by weight, relative to the total weightof these APP and HDPE, of the graft copolymer that had been prepared inExample II-5 was dissolved under heat in xylene containing 4000 ppm ofan antioxidant, BHT. The resulting mixture was re-precipitated in alarge amount of methanol, and dried to prepare a resin composition. Thiswas evaluated in the same manner as in Example II-7. Its data are shownin Table II-4.

COMPARATIVE EXAMPLE II-2 Production of Resin Composition

A resin composition was produced in the same manner as in Example II-9,for which, however, the graft copolymer of Example II-5 was not used.Its data are shown in Table II-4.

EXAMPLE II-10 Production of Resin Composition

A resin composition was produced in the same manner as in Example II-7,for which, however, used was the graft copolymer of Example II-6 inplace of that of Example II-4. Its data are shown in Table II-4.

COMPARATIVE EXAMPLE II-3 Production of Resin Composition

A resin composition was produced in the same manner as in Example II-7,for which, however, a sample A prepared in the manner mentioned belowwas used in place of the graft copolymer of Example II-4. Its data areshown in Table II-4.

Sample A:

This is a polymer prepared according to the process of Example II-2 inJapanese Patent Laid-Open No. 23017/1988.

TABLE II-4 (1) Example 7 Example 8 Co. Ex. 1 IPP (wt. %) 90 90 90 APP(wt. %) 10 10 10 HDPE (wt. %) — — — Type of Graft Example 4 Example 4 —Copolymer (wt. pts.) 5.0 10 Relaxation Rate (1/R₁) (1/sec) 1.45 1.50 —Relaxation Rate (1/R₁)₀ — — 1.40 (1/sec) Relaxation Rate Ratio [(1/R₁)/1.04 1.07 — (1/R₁)₀]

TABLE II-4 (1) Example 9 Co. Ex. 2 Example 10 Co. Ex. 3 ResinComposition IPP (wt. %) — — 90 90 APP (wt. %) 10 10 10 10 HDPE (wt. %)90 90 — — Type of Graft Example 5 — Example 6 Sample A Copolymer (wt.pts.) 5.0 5.0 5.0 Relaxation Rate 1.60 — 1.45 1.40 (1/R₁) (1/sec)Relaxation Rate — 1.52 — — (1/R₁)₀ (1/sec) Relaxation Rate Ratio 1.05 —1.04 1.00 [(1/R₁) (1/R₁)₀]

EXAMPLE II-11 Production of Ethylene Graft Copolymer

An ethylene graft copolymer was produced in the same manner as inExample II-5, for which, however, used was the macromonomer prepared inExample II-1 (2). Its yield was 35 W g. Its analysis gave the followingdata.

-   -   Intrinsic viscosity [η]: 1.50 dl/g    -   Macromonomer content: 0.8% by weight    -   Mw/Mn: 2.2    -   Melting point: 132° C.

EXAMPLE II-12 Production of Olefin Resin Composition

(1) Production of Propylene/ethylene Copolymer:

In a nitrogen atmosphere, 400 ml of dewatered heptane, 1 mmol oftriisobutylaluminium, and 0.5 mmols of ALBEMARLE's methylaluminoxanewere put into a 1.6-liter stainless pressure autoclave equipped with astirrer, and kept at 30° C. Propylene gas/ethylene gas in a molar ratioof 3.0/2.4 was introduced into this to have a controlled pressure of 0.5MPaG.

1.0 ml of a toluene solution of 0.1 μmols ofracemi-dimethylsilylbis[2-methyl-4-phenyl-indenyl]zirconium dichloride[rac-SiMe₂-(2-Me-4-Ph-Ind)₂ZrCl₂] was added to this, and the monomerswere copolymerized. After copolymerized for 10 minutes, the reactionmixture was put into a large amount of methanol, and filtered to recoverthe ethylene/propylene copolymer.

Its yield was 16.1 g. The ethylene content of the copolymer was 22 mol%; and the intrinsic viscosity [η] thereof was 1.1.

(2) Preparation of Olefin Resin Composition:

In the same manner as in Example II-7 (1), an olefin resin compositionwas prepared, for which, however, 3 parts by weight of the ethylenegraft copolymer of Example II-11 was added to 100 parts by weight of apolymer mixture comprised of 90% by weight of high-density polyethylene(Idemitsu Petrochemical Is 440M) and 10% by weight of theethylene/propylene copolymer prepared in the above (1).

(3) Evaluation of Olefin Resin Composition:

The olefin resin composition was evaluated according to “Analysis ofOlefin Resin Composition” mentioned above, and its data are shown inTable II-5.

EXAMPLE II-13 Production of Olefin Resin Composition

(1) Production of Low-stereospecificity Polypropylene:

<1> Preparation of Magnesium Compound:

A glass reactor having a capacity of about 6 liters and equipped with astirrer was fully purged with nitrogen gas. About 2430 g of ethanol, 16g of iodine and 160 g of metal magnesium were put into it, heated withstirring, and reacted under reflux until no hydrogen gas went out of thesystem, to thereby form a solid reaction product. The reaction liquidcontaining the solid product was dried under reduced pressure, and amagnesium compound was thus obtained.

<2> Preparation of Solid Catalyst Component (A):

16 g of the magnesium compound obtained in the above <1>, 80 ml of pureheptane, 2.4 ml of silicon tetrachloride, and 2.3 ml of diethylphthalate were put into a 0.5-liter, three-neck glass flask that hadbeen fully purged with nitrogen gas. This was kept at 90° C., and 77 mlof titanium tetrachloride was added thereto with stirring, and reactedat 110° C. for 2 hours. Then, the solid component was separated from it,and washed with pure heptane at 80° C. 122 ml of titanium tetrachloridewas further added thereto, reacted at 110° C. for 2 hours, and thenfully washed with pure heptane. Thus was obtained a solid catalystcomponent (A).

<3> Production of Low-stereospecificity Polypropylene:

20 g of polypropylene powder, 5.0 mmols of triisobutylaluminium (TIBA),0.125 mmols of 1-allyl-3,4-dimethoxybenzene (ADMB), 0.2 mmols ofdiphenyldimethoxysilane (DPDMS), and 20 ml of a heptane solutioncontaining 0.05 mmols (in terms of titanium) of the solid catalystcomponent (A) obtained in the above <2> were put into a 5-liter,stainless pressure autoclave, and this was degassed for 5 minutes. Then,propylene was introduced into it to have a total pressure of 2.8 MPa·G,and polymerized at 70° C. for 1.7 hours in a mode of vapor-phasepolymerization.

<4> Properties of Polypropylene:

The polypropylene obtained in the above <3> is a soft polypropylenehaving the following properties:

-   (i) boiling heptane-insoluble content: 62.4% by weight,-   (ii) intrinsic viscosity [η] in a solvent decalin at 135° C.: 4.27    dl/g,-   (iii) structure: composition of isotactic polypropylene and atactic    polypropylene.    (2) Preparation of Olefin Resin Composition;

An olefin resin composition was prepared in the same manner as inExample II-7 (1), for which, however, used were 100 parts by weight ofthe low-stereospecificity polypropylene obtained in the above (1) and 5parts by weight of the graft copolymer obtained in Example II-6.

(3) Evaluation of Olefin Resin Composition:

The olefin resin composition was evaluated according to “Analysis ofOlefin Resin Composition” mentioned above. Its data are shown in TableII-5.

EXAMPLE II-14 Production of Olefin Resin Composition:

(1) Production of High-rubber Block Copolymer:

<1> Production of Catalyst through Prepolymerization:

48 g of the solid catalyst component (A) prepared in Example II-13(1)<2> was put into a nitrogen-purged, 1-liter three-neck flask equippedwith a stirrer. 400 ml of dewatered heptane was added thereto. This washeated up to 40° C., and 2 mmols of triethylaluminium and 6.3 ml ofdicyclopentyldimethoxysilane were added thereto. Propylene gas wasintroduced into this under ordinary pressure, and reacted with it for 2hours. The solid component was fully washed with dewatered heptane. Thisis a solid catalyst (B).

<2> Production of High-rubber Block Polypropylene:

A 5-liter stainless autoclave equipped with a stirrer was fully purgedwith nitrogen gas, then dried, and thereafter purged with propylene gas.This was kept at 70° C., and propylene gas was introduced into it tohave an increased pressure of 0.05 MPaG. In this condition, hydrogen gaswas introduced into it to have a partial pressure of 0.9 MPaG, andpropylene gas was gradually introduced thereinto to have a furtherincreased pressure of 2.8 MPaG. Apart from this, 20 ml of heptane, 4mmols of triethylaluminium, 1 mmol of dicyclopentyldimethoxysilane, and0.02 mmols of the solid catalyst (B) were put into a 60-ml catalystsupply tube that had been purged with nitrogen gas, and these were ledinto the autoclave through the tube. In the autoclave containing them,propylene was polymerized for 60 minutes into a propylene homopolymer.

Next, the autoclave was degassed to atmospheric pressure, and thehomopolymer therein was sampled in a nitrogen atmosphere. The sample isfor measuring its intrinsic viscosity [η].

Next, the autoclave was degassed to vacuum, and ethylene/propylene gasin a ratio of 1:1 by mol was introduced thereinto to have an increasedpressure of 1.5 MPaG, and copolymerized at 70° C. for 65 minutes. Duringthe copolymerization, the pressure and the monomer flow rate were keptconstant. After this, the autoclave was degassed and cooled to roomtemperature, and the polymer powder was taken out.

Its copolymer moiety formed in the second-stage polymerization was 42.6%by weight.

The intrinsic viscosity of the homopolymer moiety of the block copolymerwas 1.0 dl/g; and that of the copolymer moiety thereof was 4.8 dl/g.

(2) Preparation of Olefin Resin Composition:

An olefin resin composition was prepared in the same manner as inExample II-7 (1), for which, however, used were 100 parts by weight ofthe high-rubber block polypropylene obtained in the above (1) and 5parts by weight of the graft copolymer obtained in Example II-4.

(3) Evaluation of Olefin Resin Composition:

The olefin resin composition was evaluated according to “Analysis ofOlefin Resin Composition” mentioned above. Its data are shown in TableII-5.

COMPARATIVE EXAMPLE II-4 Production of Olefin Resin Composition

An olefin resin composition was prepared in the same manner as inExample II-7 (1), for which, however, a polymer mixture comprised of 90%by weight of high-density polyethylene (Idemitsu Petrochemical's 440M)and 10% by weight of the ethylene/propylene copolymer prepared inExample II-12 (1) was used alone.

(1) Evaluation of Olefin Resin Composition:

The relaxation rate, (1/R₁) and (1/R₁)₀, of the olefin resin compositionwas determined according to “Analysis of Olefin Resin Composition”mentioned above. Its data are shown in Table II-5.

COMPARATIVE EXAMPLE II-5 Production of Olefin Resin Composition

An olefin resin composition was prepared in the same manner as inExample II-7 (1), for which, however, 100 parts by weight of thelow-stereospecificity polypropylene prepared in Example II-13 (1) wasused alone.

The relaxation rate, (1/R₁) and (1/R₁)₀, of the olefin resin compositionwas determined according to “Analysis of Olefin Resin Composition”mentioned above. Its data are shown in Table II-5.

COMPARATIVE EXAMPLE II-6 Production of Olefin Resin Composition

An olefin resin composition was prepared in the same manner as inExample II-7 (1), for which, however, 100 parts by weight of thehigh-rubber block polypropylene prepared in Example II-14 (1) was usedalone. The relaxation rate, (1/R₁) and (1/R₁)₀, of the olefin resincomposition was determined according to “Analysis of Olefin ResinComposition” mentioned above. Its data are shown in Table II-5.

TABLE II-5 (1) Resin Composition Example 12 Example 13 Example 14 A (wt.%) 90 — — B (wt. %) 10 — — C (wt. %) — 100 — D (wt. %) — — 100 Type ofGraft Example 11 Example 6 Example 4 Polymer (wt. pts.) 3.0 5.0 5.0Relaxation Rate (1/R₁) (1/sec) 1.52 1.47 1.57 Relaxation Rate (1/R₁)₀ —— — (1/sec) Ratio of Relaxation Rate 1.05 1.05 10.6 [(1/R₁)/((1/R₁)₀]

TABLE II-5 (2) Co. Ex. 4 Co. Ex. 5 Co. Ex. 6 A (wt. %) 90 — — B (wt. %)10 — — C (wt. %) — 100 — D (wt. %) — — 100 Type of Graft — — — Polymer(wt. pts.) Relaxation Rate (1/R₁) (1/sec) — — — Relaxation Rate (1/R₁)₀(1/sec) 1.45 1.40 1.48 Ratio of Relaxation Rate — — — [(1/R₁)/(1/R₁)₀]A: HDPE B: ethylene/propylene copolymer C: low-stereospecificitypolypropylene D: high-rubber block polypropylene

INDUSTRIAL APPLICABILITY

The olefin branched macromonomer, the propylene macromonomer, the olefingraft copolymer and the olefin resin composition of the invention havethe advantage of good compatibility with polyolefin resins, and aretherefore expected to much contribute toward expanding the applicationsof polyolefin resins in the field of compound materials. In addition,these are favorable to the field that requires high-level moldabilityand workability of resins (for example, for extrusion foaming,large-size blow molding, sheet forming, sheet working, thermoforming).

1. An olefin graft copolymer obtained by copolymerizing an atacticbranched macromonomer, wherein the macromonomer is derived from monomersselected from the group consisting of (1) propylene and (2) thecombination of propylene and at least one selected from ethylene,α-olefins having from 4 to 20 carbon atoms, cyclic olefins and styrenes,and of which the propylene content falls between 0.1 and 100 mol %, andwhich macromonomer satisfies the following (a) and (b): (a) itsweight-average molecular weight (Mw) measured through gel permeationchromatography (GPC) falls between 400 and 200000; (b) its vinyl contentis at least 70 mol % of all the unsaturated groups in the macromonomer,wherein the macromonomer satisfies each of the following (i), (ii) and(iii): (i) the ratio of the temperature dependency (E₂) of themacromonomer solution viscosity to the temperature dependency (E₁) ofthe solution viscosity of the linear polymer which has the same type ofmonomer, the same chemical composition and the same intrinsic viscosityas those of the macromonomer, E₂/E₁, satisfies the followingrelationship:1.01<E ₂ /E ₁<2.5; (ii) the ratio of the number-average molecular weightmeasured through GPC (GPC-Mn) to the number-average molecular weightmeasured through ¹³C-NMR (NMR-Mn) of the macromonomer satisfies thefollowing relationship:(GPC-Mn)/(NMR-Mn)>1; (iii) the macromonomer has branches existing not atthe α- and/or β-substituents of the monomer that constitutes themacromonomer, and the number of the branches falls between 0.01 and 40in one molecule of the macromonomer, with at least one comonomerselected from ethylene, propylene, α-olefins having from 4 to 20 carbonatoms, cyclic olefins and styrenes, in the presence of a metallocenecatalyst.
 2. The olefin graft copolymer as claimed in claim 1, whichsatisfies the following (1) and/or (2): (1) its intrinsic viscosity [η]measured in a solvent decalin at 135° C. falls between 0.3 and 15 dl/g;(2) it contains from 0.01 to 70% by weight of repeat units derived fromthe atactic branched macromonomer satisfying the following (a) and (b):(a) its weight-average molecular weight (Mw) measured through gelpermeation chromatography (GPC) falls between 400 and 200000; (b) itsvinyl content is at least 70 mol % of all the unsaturated groups in themacromonomer.
 3. An olefin resin composition comprising 100 parts byweight of a thermoplastic resin, and from 0.05 to 70 parts by weight ofthe olefin graft copolymer of claim
 1. 4. The olefin resin compositionas claimed in claim 3, of which the relaxation rate of the long-termrelaxation component measured through solid ¹H-NMR (1/R₁) falls between1.0 and 2.0 (1/sec).
 5. An olefin graft copolymer obtained bycopolymerizing an atactic propylene macromonomer satisfying thefollowing (a), (b) and (c): (a) its weight-average molecular weight (Mw)measured through gel permeation chromatography (GPC) falls between 800and 500000; (b) its vinyl content is at least 70 mol % of all theunsaturated groups in the macromonomer; (c) its propylene content fallsbetween 50 and 100 mol %, with at least one comonomer selected fromethylene, propylene, α-olefins having from 4 to 20 carbon atoms, cyclicolefins and styrenes, in the presence of a metallocene catalyst, whicholefin graft copolymer satisfies the following (1), (2), (3) and (4):(1) its intrinsic viscosity [η] measured in a solvent decalin at 135° C.falls between 0.7 and 12 dl/g; (2) the ratio of the weight-averagemolecular weight (Mw) to the number-average molecular weight (Mn)thereof measured through GPC, Mw/Mn, falls between 1.5 and 3.0; (3) itcontains from 0.01 to 40% by weight of repeat units derived from thepropylene atactic macromonomer; (4) it has no terminal vinyl group inthe olefin graft copolymer.
 6. An olefin resin composition comprising100 parts by weight of a thermoplastic resin, and from 0.05 to 70 partsby weight of the propylene graft copolymer of claim
 5. 7. The olefinresin composition as claimed in claim 6, of which the relaxation rate ofthe long-term relaxation component measured through solid ¹H-NMR (1/R₁)falls between 1.0 and 2.0 (1/sec).
 8. An olefin resin compositioncomprising 100 parts by weight of a thermoplastic resin, and from 0.05to 70 parts by weight of the olefin graft copolymer of claim
 2. 9. Theolefin resin composition as claimed in claim 8, of which the relaxationrate of the long-term relaxation component measured through solid ¹H-NMR(1/R₁) falls between 1.0 and 2.0 (1/sec).
 10. The olefin resincomposition as claimed in claim 8, of which the ratio of the relaxationrate of the long-term relaxation component measured through solid ¹H-NMR(1/R₁) falls between 1.0 and 2.0 (1/sec) to the relaxation rate (1/R₁)₀of the long-term relaxation component, measured through solid ¹H-NMR, ofa resin composition not containing the propylene branched macromonomer,[(1/R₁)/(1/R₁)₀] satisfying the following (a) and (b): (a) itsweight-average molecular weight (Mw) measured through gel permeationchromatography (GPC) falls between 400 and 200000, (b) its vinyl contentis at least 70 mol % of all the unsaturated groups in the macromonomer,[(1/R₁)/(1/R₁)₀], satisfies the following relationship:[(1/R ₁)/(1/R ₁)₀]>1.01.